Gas barrier film and electronic device using the same

ABSTRACT

Provided is a gas barrier film, which has sufficient bending property, transparency, barrier performance, and durability. 
     The gas barrier film includes a substrate, and a gas barrier unit being arranged on at least one side of the substrate, wherein the gas barrier unit includes a first barrier layer including an inorganic substance, a second barrier layer obtained by performing a conversion treatment to a coating film formed by coating polysilazane onto the first barrier layer, and a third barrier layer including an inorganic substance in order.

TECHNICAL FIELD

The present invention relates to a gas barrier film having a high gasbarrier property, and specifically, to a gas barrier film having a highgas barrier property, which is suitable for coating base materials ofvarious devices or base materials. In addition, the present inventionrelates to an electronic device, especially, an organicelectroluminescence element (hereinafter, referred to as “an organic ELelement”), such as an image display element using the gas barrier film.

BACKGROUND ART

Conventionally, a gas barrier film prepared by forming a thin film ofmetal oxide such as aluminum oxide, magnesium oxide, or silicon oxide onthe surface of a plastic substrate or a film has been extensively usedfor packaging purposes to package the products that require blocking ofvarious types of gases such as water vapor and oxygen, for example, forpackaging purposes to package the foods, industrial products, andpharmaceutical products to prevent them from being deteriorated. Inaddition to packaging purposes, a gas barrier film is being used for aliquid crystal display element, a solar cell, an EL substrate, and thelike. Especially, recently, as a result of reviewing the application ofa gas barrier film to a liquid crystal display element, an organic ELelement, and the like, high demands such as high long-term reliability,high flexibility of a shape, and a display practicable on a curvedsurface are further required as well as the demands for weightlightening or enlargement. For this reason, instead of a glass substratewhich is heavy, easily broken, and is difficult to have a large area,the use of a film substrate such as a transparent plastic is started. Aplastic film satisfies the above demands, and also can use aroll-to-roll way, so that as compared with glass, the productivitythereof is high, and also it is an advantage for a cost cutting.

However, a film substrate such as a transparent plastic has a problem inthat a gas barrier property is deteriorated in comparison with glass.When using the substrate having a low gas barrier property, water vaporor air is permeated thereto, and thereby, for example, a liquid crystalin a liquid crystal cell is deteriorated and a display defect isgenerated, and thus, the display quality is deteriorated. In order tosolve the above problems, it is known that a metal oxide thin film isformed on a film substrate to be a gas barrier film substrate. As a gasbarrier film used for a packaging material or a liquid crystal displayelement, a plastic film having a deposited silicon oxide thereon (seeJapanese Examined Patent Application No. 53-12953) and a plastic filmhaving a deposited aluminum oxide thereon (see Japanese PatentApplication Laid-Open No. 58-217344) are known, in which all of theabove plastic films have a water vapor barrier property of about 1g/m²·day.

However, recently, by enlarging a liquid crystal display and developinga high definition display, higher barrier performance is being demandedof a film substrate. Especially, recently, the development of an organicEL display or high vividness color liquid crystal display that requiresa further higher barrier property is in progress, so that a filmsubstrate having further higher barrier performance while maintainingthe transparency that can be used therefor, especially, a film substratehaving water vapor barrier performance of less than 0.1 g/m²·day isbeing required. In order to respond to the above demands, a film-formingmethod by a CVD method or a sputtering method for forming a thin filmusing the plasma generated by performing a glow discharge under alow-pressure condition is being reviewed as a way having an expectationfor higher barrier performance. In addition, a technique formanufacturing a barrier film having an alternative lamination structureof an organic layer/inorganic layer by a vacuum evaporation method hasbeen proposed (see Specification of U.S. Pat. No. 6,413,645 andAffinito, et al., Thin Solid Film, 290-291 (1996)).

SUMMARY OF INVENTION Technical Problem

A gas barrier film also requires bending resistance or transparency aswell as the water vapor barrier performance described above. However,the conventional gas barrier films are not enough from the viewpoint ofthe bending resistance and transparency. In addition, when an electronicdevice using a gas barrier film is installed under a high-temperatureand high-humidity environment, there was a problem such as adeterioration of a device due to a decrease of a gas barrierperformance. For this reason, an improvement of durability under ahigh-temperature and high-humidity environment is required.

Accordingly, an object of the present invention is to provide a gasbarrier film having sufficient bending resistance, transparency, andwater vapor barrier performance. In addition, another object of thepresent invention is to provide an electronic device having excellentdurability under a high-temperature and high-humidity and capable ofbeing weight lightening.

Solution to Problem

The above objects are achieved by the following present invention. Inother words, the present invention relates to a gas barrier filmincluding a substrate and a gas barrier unit being arranged on at leastone side of the substrate, in which the gas barrier unit includes afirst barrier layer including an inorganic substance, a second barrierlayer obtained by performing a conversion treatment to a coating filmthat is formed by coating polysilazane onto the first barrier layer, anda third barrier layer including an inorganic substance in order.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram illustrating an example of a vacuum plasmaCVD apparatus used for forming a first layer according to the presentinvention.

DESCRIPTION OF EMBODIMENTS

A gas barrier film according to the present invention includes asubstrate, and a gas barrier unit that is constituted by being arrangedon at least one side of the substrate, in which the gas barrier unitincludes a first barrier layer including an inorganic substance, asecond barrier layer obtained by performing a conversion treatment to acoating film that is formed by coating polysilazane onto the firstbarrier layer, and a third barrier layer including an inorganicsubstance in order. Hereinafter, a layer including an inorganicsubstance is also referred to as an inorganic substance layer, and alayer obtained by performing a conversion treatment to a coating filmformed by coating polysilazane is also referred to as a polysilazanelayer.

By constituting a gas barrier film as described above, a gas barrierfilm, which is flexible, has sufficient barrier performance, and hashigh transparency, can be provided. In addition, an electronic devicehaving both of durability and a weight lightening can be provided.

It is estimated that the mechanism having the above effect is asfollows. In addition, the present invention is not limited to thefollowing mechanism.

The gas barrier film according to the present invention has athree-layer structure, that is, an inorganic substance layer/apolysilazane layer/an inorganic substance layer. For the presentinvention, a three-layer structure is used from the viewpoint of abending resistance. For a layer hardness, the hardness of an inorganicsubstance layer is higher than that of a polysilazane layer, and thus,the three-layer structure is a structure that a soft polysilazane layeris inserted between the hard inorganic substance layers from theviewpoint of the hardness. In the state of repeating the bending of afilm many times, as the hardness of an upper layer nearly correspondswith the hardness of a lower layer, the timing of the shrinkage or theextending is nearly coincident, and thus, a polysilazane conversionlayer, that is, an intermediate layer, may tolerate deflection at thetime of bending. Therefore, it is believed that by constituting asymmetrical layer having a polysilazane layer as the center, a bendingresistance can be improved.

Here, the present invention is characteristic of using a polysilazanelayer as an intermediate layer that is inserted between the inorganicsubstance layers.

The present inventors repeated various examinations about the causeswhich damage a barrier performance in the conventional gas barrierfilms. As a result, it was found that a micro defect of an inorganicbarrier layer at the time of installing a thin film is the main factor.The decrease of the gas barrier performance caused by such a microdefect is getting serious under a high-temperature and high-humidity,thereby affecting the device performance.

The gas barrier film according to the present invention has veryexcellent gas barrier performance. The gas barrier film according to thepresent invention includes the first barrier layer on the substrate, andalso the second barrier layer formed with polysilazane. It is believedthat the second barrier layer blocks gas that has passed through a microdefect of the first barrier layer, and repairs the micro defect byfilling the micro defect with a coating solution of polysilazane at thetime of manufacturing a film, and therefore, cracks that are generatedfrom the micro defect as the starting point at the time of bending aredecreased. Therefore, since the second barrier layer is obtained byperforming the conversion treatment to the coating film formed withpolysilazane, gas barrier performance is improved and bending resistanceis also improved as compared with the silicon oxide film or organiclayer obtained by deposition, and the like. In addition, by using apolysilazane layer as a second layer, the transparency of the whole filmis improved. It is believed that this is because the surfaceirregularity of the first barrier layer is planarized by applying acoating solution of polysilazane, and thereby the diffused reflectioncaused by the surface irregularity of the first barrier layer can bereduced.

In addition, it can be confirmed that the gas barrier film according tothe present invention has improved durability under a high-temperatureand high-humidity condition. There are some cases that under ahigh-temperature and high-humidity condition, external force may beapplied on a gas barrier layer by a shape change (shrinkage orexpansion) of the substrate due to the change of a temperature orhumidity. At this time, it is believed that when the gas barrier layerhas a micro defect, the cracks are further enlarged from the microdefect as the starting point by the external force, so that the gasbarrier performance cannot be maintained. It is believed that the secondlayer obtained by converting polysilazane is present in this invention,and thus, the polysilazane repairs such a micro defect, so that thedurability of a film or an electronic device using the film is improvedeven under a high-temperature and high-humidity condition. In addition,under a high-temperature and high-humidity condition, there are somecases that the substrate is expanded by the change of a temperature orhumidity described above. In this case, since the layer constituent ofthe first layer of an inorganic substance has entirely different fromthe layer constitution of the second layer, that is, a polysilazaneconversion layer, and thus, the degrees of the expansions of the layersare entirely different each other, it causes cracks in some cases. Forthis reason, by inserting the second layer between the first layer andthird layer, both of which have the inorganic substances as a layerconstitution, the upper and lower layers of the second layer exhibit thesame behavior according to the expansion of the substrate under ahigh-temperature and high-humidity condition. For this reason, it isbelieved that the cracks are inhibited, and thus, the durability of thefilm is improved under a high-temperature and high-humidity condition.

Hereinafter, the gas barrier film and electronic device according to thepresent invention will be described in detail. The explanation of theconstitutional elements to be described below is based on therepresentative embodiments of the present invention, but the presentinvention is not limited to such embodiments.

<Gas Barrier Film>

The preferred embodiment of the gas barrier film according to thepresent invention will be described.

The gas barrier film includes the gas barrier unit formed on thesubstrate, in which the gas barrier unit includes the first barrierlayer/the second barrier layer obtained by performing a conversiontreatment to a coating film formed by coating polysilazane/the thirdbarrier layer. Preferably, the gas barrier unit consists of the firstbarrier layer, the second barrier layer, and the third barrier layer.

The number of the gas barrier units may be at least 1, and preferably inthe range of 1 to 10 considering the transparency. In addition, sincethe gas barrier performance, especially, the water vapor barrierperformance is improved, the film prepared by repeatedly arranging thegas barrier units is preferable. In this case, the preferred laminationnumber of the units is in the range of 2 to 5. In addition, in the casewhere the plurality of gas barrier units are present, it is preferableto share a barrier layer between the adjacent gas barrier units. Indetail, in the case of two barrier units, for example, there may be alamination type of a first barrier layer/a second barrier layer/a thirdbarrier layer (a first barrier layer)/a second barrier layer/a thirdbarrier layer.

<First Barrier Layer and Third Barrier Layer>

The first barrier layer and the third barrier layer include an inorganicsubstance. Hereinafter, the first and third barrier layers are referredto as an inorganic layer as a generic term.

The inorganic substance included in the first barrier layer and thethird barrier layer is not particularly limited, but examples thereofmay include metal oxide, metal nitride, metal carbide, metal oxynitride,or metal oxycarbide. Among them, from the viewpoint of the gas barrierperformance, it is preferable to use oxide, nitride, carbide,oxynitride, or oxycarbide, including one or more of the metals selectedfrom Si, Al, In, Sn, Zn, Ti, Cu, Ce, and Ta; is more preferable to useoxide, nitride, or oxynitride of the metal selected from Si, Al, In, Sn,Zn, and Ti; and is still more preferable to use oxide, nitride, oroxynitride of at least one of Si and Al. In detail, examples of thepreferred inorganic substance may include silicon oxide, siliconnitride, silicon oxynitride, aluminum oxide, and aluminum silicate.

Examples of the more preferred oxynitride may include silicon oxynitridefrom the viewpoint of barrier performance. Here, silicon oxynitrideindicates a composition composed of silicon, oxygen, and nitrogen asmain constituent elements. In addition to the above main constituentelements, the constituent elements such as a small amount of hydrogen,carbon, and the like that are incorporated from a substrate atmosphereor the materials for forming a film are desirably included in the amountof less than 5%, respectively. The component ratio of silicon, oxygen,and nitrogen that constitute silicon oxynitride is preferably x/y=0.2 to5.5 in the case where a component equation represents SiO_(x)N_(y). Whenx/y is 5.5 or less, it is further easy to obtain sufficient gas barrierability. In addition, when x/y is 0.2 or more, delamination between theadjacent layers is difficultly generated, and thus, it is easy to becomea film that is preferably applicable for roll conveyance and the bendinguse. The value of x/y is more preferably 0.3 to 4.5 in view of watervapor permeability and a bending property. In addition, the values of xand y are preferably a combination to be (2x+3y)/4=0.8 to 1.1. When itis 0.8 or more, coloring is inhibited, and thus, a film is easily usedas an extensive use. When it is 1.1 or less, a ratio of the constituentelements of silicon, nitrogen, and oxygen is high, and thus, a defectratio is easily inhibited, and thereby more sufficient gas barrierability can be expected. The combination to be (2x+3y)/4 of 0.85 to 1.1is more preferable.

For SiO_(x)N_(y), a method of controlling the values of x and y, isperformed by controlling flow rates of a source gas and decomposing gasusing a vacuum plasma CVD method as described below, for example. Theflow rates of the source gas and decomposing gas may be properly set inview of devices, and the like to be used.

In addition, an element constitution ratio of a laminated sample may bemeasured by the well-known standard method by X-ray photoelectronspectroscopy (XPS) while being etched.

The content of the inorganic substance included in the first barrierlayer or the third barrier layer is not particularly limited, butpreferably 50 mass % or more, more preferably 80 mass % or more, stillmore preferably 95 mass % or more, particularly preferably 98 mass % ormore, and most preferably 100 mass % (in other words, the first barrierlayer and third barrier layer are constituted of inorganic substances)in the first barrier layer or the third barrier layer.

The refractive index of the inorganic layer is preferably 1.7 to 2.1 andmore preferably 1.8 to 2.0. Especially, when it is 1.9 to 2.0, visibletransmittance is high and high gas barrier ability is stably obtained,and thus, it is most preferable.

The smoothness of the inorganic layer formed according to the presentinvention is preferably less than 1 nm and more preferably 0.5 nm orless as an average roughness (an Ra value) of 1 μm square.

The film formation of the inorganic layer is preferably performed in aclean room. The degree of the cleaning is preferably class 10000 or lessand more preferably class 1000 or less.

The thickness of the inorganic layer is not particularly limited, butgenerally in the range of 5 to 500 nm and preferably 10 to 200 nm.

The first barrier layer and third barrier layer may be a laminationstructure that is constituted of a plurality of sub-layers. In thiscase, the respective sub-layers may have the same components ordifferent components from each other. When the inorganic layer includesthe sub-layers, the number of the sub-layers is generally about 2 to 3layers.

In addition, the compositions of two inorganic layers (the first barrierlayer and the third barrier layer) that constitute the unit of thepresent invention may be the same with or different from each other.

As a method for forming an inorganic layer, any kinds of methods can beused as long as the method can form a thin film to be desired. Amongthem, the first and third barrier layers are preferably formed by anyone method of a chemical vapor deposition method, a physical vapordeposition method, and an atomic layer deposition method. According tothe present invention, the second barrier layer is obtained byconverting polysilazane. By forming the first and third barrier layersusing the mechanism that is different from that of the second barrierlayer, the film formation states of the adjacent layers may be differentfrom each other. In this way, the gas passages in the layer for theadjacent layers become different from each other, and thus, the gasbarrier performance is more improved.

In addition, the first and third barrier layers may be formed by thefilm-forming methods that are different from each other, but from theviewpoint of productivity, is preferably formed by the same film-formingmethod. In addition, the first barrier layer may be formed on thesubstrate and the third barrier layer may be formed on the secondbarrier layer.

The physical vapor deposition (PVD) method is a method for depositing adesired substance, for example, a thin film such as a carbon film on asurface of a substance in a gas phase by a physical way, and examplesthereof may include a sputtering method (a DC sputtering, an RFsputtering, an ion beam sputtering, a magnetron sputtering, and thelike), a vacuum vapor deposition method, an ion plating method, and thelike.

The sputtering method is a method including installing a target in avacuum chamber, smashing a rare gas element (generally, argon) ionizedby applying high voltage against the target, and bouncing the atom onthe surface of the target and then attaching the atom to the substrate.In this case, a reactive sputtering method may be used, in which byflowing a nitrogen gas or oxygen gas in the chamber, the element thatbounces off the target by an argon gas is reacted with nitrogen andoxygen, thereby forming an inorganic layer.

Meanwhile, a chemical vapor deposition (a chemical vapor phase growthmethod) is a method of supplying a source gas including the componentsof a thin film to be desired on a substrate and depositing a film by achemical reaction on a surface of a substrate or gas phase. In addition,in order to activate a chemical reaction, there may be a method ofgenerating plasma, and examples thereof may include the known CVDmethods such as a thermal CVD method, a catalytic chemical vapor phasegrowth method, a light CVD method, a vacuum plasma CVD method, and anatmospheric plasma CVD method. A plasma CVD method is preferably usedfrom the viewpoint of a film-forming rate or treatment area, but thepresent invention is not particularly limited thereto. A gas barrierlayer obtained by a vacuum plasma CVD method or a plasma CVD methodunder the pressure of atmosphere or near atmosphere is preferablebecause it can prepare the desired compound by selecting the conditionssuch as a metal compound that is a material (also referred to as a rawmaterial), a decomposing gas, a decomposing temperature, and introducingpower.

As a source gas, a source gas for forming a desired inorganic layer isproperly selected, and examples thereof may include a metal compoundsuch as a silicide, a titanium compound, a zirconium compound, analuminum compound, a boron compound, a tin compound, and an organicmetal compound.

Among them, examples of a silicide may include silane, tetramethoxysilane, tetraethoxy silane, tetra n-propoxy silane, tetraisopropoxysilane, tetra n-butoxy silane, tetra t-butoxy silane, dimethyl dimethoxysilane, dimethyl diethoxy silane, diethyl dimethoxy silane, diphenyldimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane,phenyl triethoxy silane, (3,3,3-trifluoro propyl)trimethoxy silane,hexamethyl disiloxane, bis(dimethylamino)dimethyl silane,bis(dimethylamino)methylvinyl silane, bis(ethylamino)dimethyl silane,N,O-bis(trimethylsilyl)acetamide, bis(trimethylsilyl)carbodiimide,diethylamino trimethyl silane, dimethylamino dimethyl silane, hexamethyldisilazane, hexamethyl cyclotrisilazane, heptamethyl disilazane,nonamethyl trisilazane, octamethyl cyclotetrasilazane,tetrakisdimethylamino silane, tetraisocyanate silane, tetramethyldisilazane, tris(dimethylamino)silane, triethoxy fluorosilane,allyldimethyl silane, allyl trimethyl silane, benzyl trimethyl silane,bis(trimethylsilyl)acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne,di-t-butyl silane, 1,3-disilabutane, bis(trimethylsilyl)methane,cyclopenta dienyl trimethyl silane, phenyl dimethyl silane, phenyltrimethyl silane, propargyl trimethyl silane, tetramethyl silane,trimethylsilyl acetylene, 1-(trimethylsilyl)-1-propyne,tris(trimethylsilyl)methane, tris(trimethylsilyl)silane, vinyl trimethylsilane, hexamethyl disilane, octamethyl cyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethyl cyclotetrasiloxane, M silicate 51, andthe like.

Examples of an aluminum compound may include aluminum ethoxide, aluminumtriisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminums-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, and the like.

In addition, examples of a decomposing gas for obtaining an inorganiccompound by decomposing a source gas including these metals may includea hydrogen gas, a methane gas, an acetylene gas, a carbon monoxide gas,a carbon dioxide gas, a nitrogen gas, an ammonia gas, a nitrous oxidegas, a nitrogen oxide gas, a nitrogen dioxide gas, an oxygen gas, andwater vapor. In addition, the decomposing gas may be mixed with an inertgas such as an argon gas and a helium gas.

The desired barrier layer may be obtained by properly selecting adecomposing gas and a source gas including a source compound.

Hereinafter, a plasma CVD method that is a suitable type among the CVDmethods will be described in detail.

FIG. 1 is a schematic diagram illustrating an example of a vacuum plasmaCVD apparatus used for forming the first layer according to the presentinvention.

In FIG. 1, a vacuum plasma CVD apparatus 101 includes a vacuum tank 102and a susceptor 105 is placed on the bottom surface side of the insideof the vacuum tank 102. In addition, A cathode electrode 103 is placedat a position, facing the susceptor 105, on the ceiling side of theinside of the vacuum tank 102. A heat medium circulating system 106, avacuum pumping system 107, a gas introduction system 108, and a highfrequency power source 109 are placed outside the vacuum tank 102. Aheat medium is placed in the heat medium circulating system 106. Aheating cooling apparatus 160 including a pump which moves the heatmedium, a heating apparatus which heats the heat medium, a coolingapparatus which cools it, a temperature sensor with which thetemperature of the heat medium is measured, and a memory apparatus whichmemorizes a set temperature for the heat medium is disposed in the heatmedium circulating system 106.

The heating cooling apparatus 160 is constituted to measure thetemperature of the heat medium, to heat or cool the heat medium to thememorized set temperature, and to supply the heat medium to thesusceptor 105. The supplied heat medium flows into the susceptor 105,heats or cools the susceptor 105, and returns to the heating coolingapparatus 160. The temperature of the heat medium is higher or lowerthan the set temperature when this occurs, and the heating coolingapparatus 160 heats or cools the heat medium to the set temperature andsupplies the heat medium to the susceptor 105. A cooling medium iscirculated between the susceptor and the heating cooling apparatus 160in this manner and the susceptor 105 is heated or cooled by the suppliedheat medium at the set temperature.

The vacuum tank 102 is connected to the vacuum pumping system 107, and,prior to starting film formation treatment by the vacuum plasma CVDapparatus 101, the heat medium has been heated to increase itstemperature from room temperature to the set temperature whilepreevacuating the inside of the vacuum tank 102 and the heat medium atthe set temperature has been supplied to the susceptor 105. Thesusceptor 105 is at room temperature when beginning to be used and thesupply of the heat medium at the set temperature results in increase inthe temperature of the susceptor 105.

The heat medium at the set temperature is circulated for given time anda substrate 110 to be film-formed is thereafter conveyed into the vacuumtank 102 while maintaining vacuum atmosphere in the vacuum tank 102 andis placed on the susceptor 105.

A large number of nozzles (pore) are formed in the surface, facing thesusceptor 105, of the cathode electrode 103.

The cathode electrode 103 is connected to the gas introduction system108, and a CVD gas is spouted from the nozzles of the cathode electrode103 into the vacuum tank 102 with vacuum atmosphere by introducing theCVD gas from the gas introduction system 108 into the cathode electrode103.

The cathode electrode 103 is connected to the high frequency powersource 109 and the susceptor 105 and the vacuum tank 102 are connectedto a ground potential.

Plasma of the introduced CVD gas is formed by supplying the CVD gas fromthe gas introduction system 108 into the vacuum tank 102, starting thehigh frequency power source 109 while supplying the heat medium at giventemperature from the heating cooling apparatus 160 to the susceptor 105,and applying a high-frequency voltage to the cathode electrode 103. Whenin the plasma, the activated CVD gas reaches the surface of thesubstrate 110 on the susceptor 105, a first layer that is a thin film onthe surface of the substrate 110 is grown.

At this time, the distance between the susceptor 105 and the cathodeelectrode 103 is properly set.

In addition, the flow rates of the source gas and decomposing gas areproperly set in view of the kinds of the source gas and decomposing gas.

During the growth of the thin film, the thin film is formed in the statewhere the heat medium at the given temperature has been supplied fromthe heating cooling apparatus 160 to the susceptor 105 and the susceptor105 is heated or cooled by the heat medium and maintained at giventemperature. Generally, the lower limit temperature of growthtemperature at which the thin film is formed depends on the film qualityof the thin film while the upper limit temperature thereof depends onthe permissible range of damage to the thin film that has been alreadyformed on the substrate 110. The lower limit temperature or upper limittemperature depends on the material quality of the thin film beingalready formed or the material quality of the thin film to be formed,but in order to secure the film quality having high gas barrier, it ispreferable that the lower limit temperature be 50° C. or higher and theupper limit temperature be the heat-resisting temperature or less ofsubstrates.

The lower limit temperature and upper limit temperature are determinedby obtaining in advance the relation between the temperature for formingthe film and the film quality of the thin film, which is formed by avacuum plasma CVD method and the relation between the temperature forforming the film and the damage affected to the object (the substrate110) to be formed with the film. For example, the temperature of thesubstrate 110 during a vacuum plasma CVD process is preferably 50 to250° C.

Furthermore, when a high-frequency voltage of 13.56 MHz or more isapplied to the cathode electrode 103 to form plasma, the relationshipbetween the temperature of the heat medium supplied to the susceptor 105and the temperature of the substrate 110 has been premeasured and thetemperature of the heat medium supplied to the susceptor 105 has beendetermined to maintain the temperature of the substrate 110 at the lowerlimit temperature or more and the upper limit temperature or less duringthe vacuum plasma CVD process.

For example, it is set to memorize the lower limit temperature (50° C.in this case) and to supply the heat medium, of which the temperature iscontrolled to the lower limit temperature or more, to the susceptor 105.The heat medium flowing back from the susceptor 105 is heated or cooledand the heat medium at the set temperature of 50° C. is supplied to thesusceptor 105. For example, a mixed gas of silane gas and ammonia gaswith nitrogen gas is supplied as the CVD gas to form a SiN film in thestate where the temperature condition of the substrate 110 is maintainedat the lower limit temperature or more and the upper limit temperatureor less.

Immediately after starting the vacuum plasma CVD apparatus 101, thetemperature of the susceptor 105 is room temperature and the temperatureof the heating medium that is refluxed from the susceptor 105 to theheating cooling device 160 is lower than the setting temperature. Thus,immediately after the start, the heating cooling apparatus 160 heats theheat medium flowing back to increase its temperature to the settemperature and supplies the heat medium to the susceptor 105. In thiscase, the susceptor 105 and the substrate 110 are heated by the heatmedium to increase its temperature and the substrate 110 is maintainedin the range of the lower limit temperature or more and the upper limittemperature or less.

The temperature of the susceptor 105 is increased due to heat flowing infrom plasma by consecutively forming thin films on a plurality ofsubstrates 110. In this case, the heat medium flowing back from thesusceptor 105 to the heating cooling apparatus 160 has highertemperature than the lower limit temperature (50° C.) and the heatingcooling apparatus 160 therefore cools the heat medium and supplies theheat medium at the set temperature to the susceptor 105. As a result,the thin films can be formed while maintaining the substrates 110 in therange of the lower limit temperature or more and the upper limittemperature or less.

As described above, the heating cooling apparatus 160 heats the heatmedium in the case in which the temperature of the heat medium flowingback is lower than the set temperature and cools the heat medium in thecase in which the temperature thereof is higher than the settemperature, the heat medium at the set temperature is supplied to thesusceptor in both cases, and the substrate 110 is therefore maintainedin the temperature range of the lower limit temperature or more and theupper limit temperature or less.

After formation of the thin film with a predetermined film thickness,the substrate 110 is conveyed outside the vacuum tank 102, a substrate110 on which no film has been formed is conveyed into the vacuum tank102, and a thin film is formed while supplying the heat medium at theset temperature in the same manner as described above.

Generally, in the conventional organic inorganic laminated gas barrierlaminate, when the inorganic layer is formed by a physical or chemicalvapor deposition method, there is a problem in that the desired gasbarrier property cannot be obtained. It is believed that since thesputtering method or CVD method uses high-energy particles, the pinholeor damage of the produced thin film is caused.

However, since the gas barrier film of the present invention includes asecond barrier layer by applying a coating solution of polysilazane onthe inorganic layer and then conducting a conversion treatment, thepassage of the gas passing through a micro defect is blocked, and thuseven if the inorganic layer is formed by a physical or chemicaldeposition method, the high barrier property can be maintained. Inaddition, by having the third barrier layer, even after testing thebending property, the high barrier performance can be maintained.

It is preferable that the first and third layers be constituted byforming in an atomic layer deposition method.

An atomic layer deposition method (hereinafter, also referred to as “anALD method”) is a method of using a chemical adsorption and chemicalreaction of a plurality of low-energy gases to the surface of thesubstrate. Since the sputtering method or CVD method uses high-energyparticles, the pinhole or damage of the produced thin film is caused.However, such a method has an advantage in that since it uses aplurality of low-energy gases, the pinhole or damage rarely occurs, anda high-density single atom film may be obtained (Japanese PatentApplication Laid-Open No. 2003-347042, Japanese Patent ApplicationNational Publication (Laid-Open) No. 2004-535514, and InternationalPatent Publication No. 2004/105149 Pamphlet). For this reason, it ispreferable to form at least the first barrier layer, and more preferablyto form the first and third barrier layers by the ALD method since thewater vapor barrier performance (WVTR) is improved.

According to the ALD method, a single atom layer (a gas molecular layer)is formed on the substrate by changing a plurality of gases as a rawmaterial in turn and then leading the gas onto the substrate, andperforming a chemical adsorption, and an inorganic layer is formed onelayer by one layer by the chemical reaction on the substrate. In moredetail, first, the first gas is introduced onto the substrate to form agas molecular layer (a single atom layer). Subsequently, by introducinginert gases, the first gas is purged (removed). In addition, theproduced gas molecular layer of the first gas is not purged even if theinert gas is introduced due to the chemical adsorption. Subsequently,the produced gas molecular layer is oxidized by introducing the secondgas to form an inorganic film. Finally, the second gas is purged byintroducing an inert gas to complete one cycle of the ALD method. Byrepeating the above cycle, the atomic layer is deposited one layer byone layer, and thus, the first gas barrier layer having thepredetermined film thickness can be formed. In addition, according tothe ALD method, an inorganic film including a shading part can be formedwithout depending on the surface irregularity of the substrate.

The inorganic oxides formed by the ALD method is not particularlylimited, but examples thereof may include oxides of aluminum, titanium,silicon, zirconium, hafnium, and lanthanum etc. and complex oxidesthereof. It is preferable that from the viewpoint where a high qualityfilm is obtained at the temperature of 50° C. to 120° C. considering afilm formation on a resin substrate, an inorganic oxide include one ormore kinds selected from the group consisting of Al₂O₃, TiO₂, SiO₂ andZrO.

In addition, by adjusting an introduction time for each gas, afilm-formation temperature, and a pressure at the time of forming afilm, it is possible to be intermediate oxides such as AlO_(x), TiOx,SiOx, and ZrOx, nitride, and the like, and if necessary, they can beused without any problem.

Since a surface of a substrate is required to be activated in order fora gas molecule to be adsorbed onto the substrate, it is preferable thata temperature for forming a film be a high temperature to some degreeand may be properly adjusted in the range that does not exceed a glasstransition temperature or a decomposition starting temperature of aplastic substrate of substrates. In the case of using a plasticsubstrate, the temperature in a reactor generally is about 50 to 200° C.The deposition rate for one cycle generally is 0.01 to 0.3 nm, and byrepeating a cycle for forming a film, the desired thickness of the filmis obtained.

For example, when the ALD layer is an aluminum oxide layer, the firstgas is a gas obtained by evaporating an aluminum compound, and thesecond gas may be an oxidative gas. In addition, the inert gas is a gasthat does not react with the first gas and/or the second gas.

The aluminum compound is not particularly limited as long as it includesaluminum and can be evaporated. Specific examples of the aluminumcompound may include trimethyl aluminum (TMA), triethyl aluminum (TEA),and trichloroaluminum.

Furthermore, a source gas may be properly selected by an inorganic oxidefilm to be formed, and for example, the source gas disclosed in M.Ritala: Appl. Surf. Sci. 112, 223 (1997) may be used. In detail, whenthe inorganic oxide of the second layer is silicon oxide, the first gasis a gas obtained by evaporating a silicon compound. Examples of thesilicon compound may include other chlorosilane-based compounds such asmonochlorosilane (SiH₃Cl, MCS), hexachlorodisilane (Si₂Cl₆, HCD),tetrachlorosilane (SiCl₄, STC), and trichlorosilane (SiHCl₃, TCS),inorganic raw materials such as trisilane (Si₃H₈, TS), disilane (Si₂H₆,DS), and monosilane (SiH₄, MS), amino silane-based compounds such astetrakisdimethylamino silane (Si[N(CH₃)₂]4, 4DMAS), trisdimethylaminosilane (Si[N(CH₃)₂]₃H, 3DMASi), bisdiethylamino silane (Si[N(C₂H₅)₂]₂H₂,2DEAS), and bis tertiary butylamino silane (SiH₂[NH(C₄H₉)]₂, BTBAS), andthe like.

In addition, when the inorganic oxide of the second layer is titaniumoxide, the first gas is a gas obtained by evaporating a titaniumcompound. Examples of the titanium compound may include titaniumtetrachloride (TiCl₄), titanium (IV) isopropoxide (Ti[(OCH)(CH₃)₂]₄),tetrakisdimethylamino titanium ([(CH₃)₂N]₄Ti, TDMATi),tetrakisdiethylamino titanium (Ti[N(CH₂CH₃)₂]₄, TDEATi), and the like.

In addition, when the ALD layer is a zirconium oxide layer, the firstgas is a gas obtained by evaporating a zirconium compound. Examples ofthe zirconium compound may include tetrakisdimethylamino zirconium (IV);[(CH₃)₂N]₄Zr, and the like.

The oxidative gas is not particularly limited as long as it can oxidizea gas molecular layer, and examples thereof may include ozone (O₃),water (H₂O), hydrogen peroxide (H₂O₂), methanol (CH₃OH), ethanol(C₂H₅OH), and the like. In addition, it is possible to use an oxygenradical. In the case of using a radical, it is possible to generate ahigh-density oxygen radical by activating a gas using the high-frequencypower (for example, the power of frequency 13.56 MHz), and to furtherfacilitate the oxidation and nitration reaction. Considering theenlargement or practicality of a device, the electric discharge in amode of ICP (Inductively Coupled Plasma) using the powder of 13.56 MHzis preferable.

In addition, when nitride and nitrogen oxide are desired, a nitrogenradical may be used. The nitrogen radical may be produced in the sameway as the way for producing an oxygen radical.

In addition, ozone and an oxygen radical are preferably used as anoxidative gas from the viewpoint of a size of a device or a reduction ofone cycle time. In addition, an oxygen radical is preferably used fromthe viewpoint of forming a dense film at a low temperature.

As the inert gas, a rare gas (helium, neon, argon, krypton, xenon), anitrogen gas, and the like may be used.

An introduction time of the first gas is preferably 0.05 to 10 seconds,more preferably 0.1 to 3 seconds, and still more preferably 0.5 to 2seconds. When the introduction time of the first gas is 0.05 second ormore, the time capable of forming a gas molecular layer can besufficiently secured, and thus, it is preferable. Meanwhile, when theintroduction time of the first gas is 10 seconds or less, the timerequired for one cycle can be reduced, and thus, it is preferable.

In addition, the introduction time of the inert gas for purging thefirst gas is preferably 0.05 to 10 seconds, more preferably 0.5 to 6seconds, and still more preferably 1 to 4 seconds. When the introductiontime of the inert gas is 0.05 second or more, the first gas may besufficiently purged, and thus, it is preferable. Meanwhile, when theintroduction time of the inert gas is 10 seconds or less, the timerequired for one cycle can be reduced and has less of an effect on theformed gas molecular layer, and thus, it is preferable.

In addition, the introduction time of the second gas is preferably 0.05to 10 seconds, and more preferably 0.1 to 3 seconds. When theintroduction time of the second gas is 0.05 second or more, the timerequired for oxidizing the gas molecular layer can be sufficientlysecured, and thus, it is preferable. Meanwhile, the introduction time ofthe second gas is 10 seconds or less, the time required for one cyclecan be reduced and a side reaction can be prevented, and thus, it ispreferable.

In addition, the introduction time of the inert gas for purging thesecond gas is preferably 0.05 to 10 seconds. When the introduction timeof the inert gas is 0.05 second or more, the second gas can besufficiently purged, and thus, it is preferable. Meanwhile, when theintroduction time of the inert gas is 10 seconds or less, the timerequired for one cycle can be reduced and has less of an effect on theformed atomic layer, and thus, it is preferable.

<Second Barrier Layer (Hereinafter, Also Referred to as a PolysilazaneLayer)>

The second barrier layer is obtained by coating polysilazane onto thefirst barrier layer and then performing the conversion treatment to thecoating film thus formed.

For forming a polysilazane layer, as a method for coating a coatingsolution including polysilazane (hereinafter, also referred to as apolysilazane coating solution) on the first barrier layer, a proper wetcoating method that is conventionally known may be used. Specificexamples thereof may include a spin coating method, a roll coatingmethod, a flow coating method, an ink-jet method, a spray coatingmethod, a printing method, a dip coating method, a film casting method,a bar coating method, a gravure printing method, and the like.

The coating thickness may be properly set according to a purpose. Forexample, as the coating thickness, the thickness after drying ispreferably about 10 nm to 10 μm, and more preferably 50 nm to 1 μm. Whenthe film thickness of the polysilazane layer is 10 nm or more, thesufficient barrier property can be obtained. Meanwhile, when it is 10 μmor less, the stable coating property at the time of forming thepolysilazane layer can be obtained and also high light permeability canbe realized.

(Polysilazane)

Hereinafter, polysilazane will be described.

Polysilazane is a polymer having a silicon-nitrogen bond, and aprecursor inorganic polymer of a ceramic such as SiO₂ and Si₃N₄, andSiO_(x)N_(y) that is an intermediate solid solution of the both, havingSi—N, Si—H, and N—H bonds.

The polysilazane is preferably a compound having a structure representedby the following General Formula (I).

[Chemical Formula 1]

—(SiR₁R₂—NR₃)₃—  General Formula (I)

In the above General Formula (I), R₁, R₂, and R₃ are the same with ordifferent from each other, and each independently, a hydrogen atom; or asubstituted or unsubstituted alkyl group, aryl group, vinyl group, or(trialkoxysilyl)alkyl group. Here, examples of the alkyl group mayinclude a linear chain, branched, or cyclic alkyl group having 1 to 8carbon atoms. More specific examples thereof may include a methyl group,an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentylgroup, an isopentyl group, a neopentyl group, an n-hexyl group, ann-heptyl group, an n-octyl group, a 2-ethylhexyl group, a cyclopropylgroup, a cyclopentyl group, a cyclohexyl group, and the like. Inaddition, examples of the aryl group may include an aryl group having 6to 30 carbon atoms. More specific examples thereof may include anon-condensed hydrocarbon group such as a phenyl group, a biphenylgroup, and a terphenyl group; and a condensed polycyclic hydrocarbonsgroup such as a pentalenyl group, an indenyl group, a naphthyl group, anazulenyl group, a heptalenyl group, a biphenylenyl group, a fluorenylgroup, an acenaphthylenyl group, a pleiadenyl group, an acenaphthenylgroup, a phenalenyl group, a phenanthryl group, an anthryl group, afluoranthenyl group, an acephenanthrylenyl group, an aceanthrylenylgroup, a triphenylenyl group, a pyrenyl group, a chrysenyl group, and anaphthacenyl group. Examples of the (trialkoxysilyl)alkyl group mayinclude an alkyl group having 1 to 8 carbon atoms that has a silyl groupsubstituted with an alkoxy group having 1 to 8 carbon atoms. Morespecific examples thereof may include a 3-(triethoxysilyl)propyl group,a 3-(trimethoxysilyl)propyl group, and the like. In the cases of the R₁to R₃, a substituent that is present according to circumstances is notparticularly limited, but for example, an alkyl group, a halogen atom, ahydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), asulfo group (—SO₃H), a carboxyl group (—COOH), a nitro group (—NO₂), andthe like. In addition, a substituent that is present according tocircumstances may not be the same as R₁ to R₃ to be substituted. Forexample, when R₁ to R₃ are an alkyl group, it is not further substitutedwith an alkyl group. Among them, preferably, R₁, R₂, and R₃ are ahydrogen atom, a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a tert-butyl group, aphenyl group, a vinyl group, a 3-(triethoxysilyl)propyl group or a3-(trimethoxysilylpropyl) group. Preferably, R₁, R₂ and R₃ eachindependently are a group selected from the group consisting of ahydrogen atom, a methyl group, an ethyl group, a propyl group, aniso-propyl group, a butyl group, an iso-butyl group, a tert-butyl group,a phenyl group, a vinyl group, a 3-(triethoxysilyl)propyl group and a3-(trimethoxysilyl)propyl group.

In addition, in the above General Formula (I), n is an integer, and n isdetermined such that the polysilazane having the structure representedby General Formula (I) has an number average molecular weight of 150 to150,000 g/mole.

For the compound having the structure represented by General Formula(I), one of preferred embodiments is a perhydropolysilazane, in whichall of R₁, R₂, and R₃ are hydrogen atoms from the viewpoint of a denseproperty of the obtained polysilazane layer. It is estimated thatperhydropolysilazane has a structure having a linear chain structure anda ring structure having 6- and 8-membered ring as a center. Themolecular weight thereof is about 600 to 2000 (polystyrene conversion)as a number average molecular weight (Mn), and it is a liquid or solidsubstance, and the state thereof depends on the molecular weight.

In addition, the polysilazane according to the present invention ispreferably a compound having a structure represented by the followingGeneral Formula (II).

[Chemical Formula 2]

—[Si(R_(1′))(R_(2′))—N(R_(3′))]_(n′)—[Si(R_(4′))(R_(5′))—N(R_(6′))]_(n′)  GeneralFormula (II)

In the above General Formula (II), R_(1′), R_(2′), R_(3′), R_(4′),R_(5′), and R_(6′), each independently are a hydrogen atom; and asubstituted or unsubstituted alkyl group, aryl group, vinyl group, or(trialkoxysilyl)alkyl group. At this time, R_(1′), R_(2′), R_(3′),R_(4′), R_(5′), and R_(6′), may be the same with or different from eachother, respectively. The description on the substituted or unsubstitutedalkyl group, aryl group, vinyl group, or (trialkoxysilyl)alkyl group isthe same as the definition in General Formula (I), and thus, will not beprovided. n′ and p are an integer, and determined such that thepolysilazane having the structure represented by General Formula (II)has a number average molecular weight of 150 to 150,000 g/mole. Inaddition, n and p may be the same with or different from each other.

In General Formula (II), a compound in which R_(1′), R_(3′), and R_(6′),are a hydrogen atom, respectively, R_(2′), R_(4′), and R_(5′), are amethyl group, respectively; a compound in which R_(1′), R_(3′), andR_(6′) are a hydrogen atom, respectively, R_(2′), and R_(4′), are amethyl group, respectively, and R_(5′) is a vinyl group; and a compoundin which R_(1′), R_(3′), R_(4′), and R_(6′) are a hydrogen atom,respectively, and R_(2′) and R_(5′) are a methyl group, respectively aremore preferable.

In addition, polysilazane is preferably a compound having the structurerepresented by the following General Formula (III).

[Chemical Formula 3]

—[Si(R_(1″))(R_(2″))—N(R_(3″))]_(n″)—[Si(R_(4″))(R_(5″))—N(R_(6″))]_(p″)—[Si(R_(7″)(R_(8″))—N(R_(9″))]_(q)  GeneralFormula (III)

In the above General Formula (III), R_(1″), R_(2″), R_(3″), R_(4″),R_(5″), R_(6″), R_(7″), R_(8″), and R_(9″) each independently are ahydrogen atom; or a substituted or unsubstituted alkyl group, arylgroup, vinyl group, or (trialkoxysilyl)alkyl group. At this time,R_(1″), R_(2″), R_(3″), R_(4″), R_(5″), R_(6″), R_(7″), R_(8″), andR_(9″) may be the same with or different from each other, respectively.The description about the above substituted or unsubstituted alkylgroup, aryl group, vinyl group, or (trialkoxysilyl)alkyl group is thesame as the definition of the above General Formula (I), and thus, willnot be provided. n″, p″ and q are an integer, respectively, and isdetermined such that the polysilazane having the structure representedby General Formula (III) has a number average molecular weight of 150 to150,000 g/mole. The description about the above substituted orunsubstituted alkyl group, aryl group, vinyl group, or(trialkoxysilyl)alkyl group is the same as the definition of the aboveGeneral Formula (I), and thus, will not be provided. In addition, n″, p″and q may be the same with or different from each other.

In the above General Formula (III), a compound in which R_(1″), R_(3″),and R_(6″) are a hydrogen atom, respectively, R_(2″), R_(4″), R_(5″),and R_(8″) are a methyl group, respectively, and R_(9″) is a(triethoxysilyl)propyl group, and R_(7″) is an alkyl group or a hydrogenatom is particularly preferable.

Meanwhile, organopolysilazane, in which a part of a hydrogen atom partbound to Si is substituted with an alkyl group, and the like, hasadvantages in that an adhesive property with a substrate that is a basisis improved by having an alkyl group such as a methyl group, toughnesscan be applied on a ceramic film by the hard and fragile polysilazane,and a generation of cracks is suppressed even in the case of havingthicker (average) film thickness. The perhydropolysilazane andorganopolysilazane may be properly selected according to the usethereof, or may be mixed and then used.

Other examples of the polysilazane compound may include polysilazane,which becomes a ceramic at a low temperature, such as silicon alkoxideaddition polysilazane obtained by reacting the polysilazane with siliconalkoxide (Japanese Patent Application Laid-Open No. 5-238827), glycidoladdition polysilazane obtained by reacting the polysilazane withglycidol (Japanese Patent Application Laid-Open No. 6-122852), alcoholaddition polysilazane obtained by reacting the polysilazane with alcohol(Japanese Patent Application Laid-Open No. 6-240208), metal carbonateaddition polysilazane obtained by reacting the polysilazane with metalcarbonate (Japanese Patent Application Laid-Open No. 6-299118), acetylacetonate complex addition polysilazane obtained by reacting thepolysilazane with acetyl acetonate complex including metals (JapanesePatent Application Laid-Open No. 6-306329), and metal fine particlesaddition polysilazane obtained by adding metal fine particles (JapanesePatent Application Laid-Open No. 7-196986).

A solvent can be used in a coating solution with a formation of thepolysilazane layer, and as a rate of the polysilazane in the solvent,the polysilazane is generally 1 to 80 mass %, preferably 5 to 50 mass %,and more preferably 10 to 40 mass %.

Especially, as a solvent, an organic-based solvent that does not includewater and a reactive group (for example, a hydroxyl group or an aminegroup) and is inert to polysilazane is preferable, and a non-protonicsolvent is preferable.

A solvent capable of being applied for a polysilazane coating solutionaccording to the present invention may be a non-protonic solvent;hydrocarbon solvents, for example, aromatic hydrocarbon, aliphatichydrocarbon such as pentane, hexane, cyclohexane, toluene, xylene,solvesso, and turpentine, and the like; halogen hydrocarbon solventssuch as methylene chloride and trichloroethane; esters such as ethylacetate and butyl acetate; ketones such as acetone and methylethylketone; and for example, tetrahydrofuran, dibutyl ether, mono- andpolyalkylene glycol dialkylether (diglymes) ethers, or mixture of thesesolvents. The solvents are selected to suit the purposes such as thesolubility of polysilazane or the evaporating rate of a solvent, and maybe used singly or in combination of two or more kinds thereof.

Polysilazane is available in the market in a state of solution dissolvedin an organic solvent, and a product on the market can be directly usedas a coating solution including polysilazane. Examples of the product onthe market may include AQUAMICA (Registered trademark) NN120-10,NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110,NP140, SP140, and the like, manufactured by AZ Electronic Material.

The polysilazane coating solution may include a catalyst along withpolysilazane. The applicable catalyst is preferably a basic catalyst,and especially, N,N-diethyl ethanolamine, N,N-dimethyl ethanolamine,triethanolamine, triethylamine, 3-morpholino propylamine orN-heterocyclic compound is preferable. The concentration of the catalystadded is generally in the range of 0.1 to 10 mol % and preferably 0.5 to7 mol % based on polysilazane.

For the polysilazane coating solution, the additives that areexemplified hereinafter can be used if necessary. Examples thereof mayinclude cellulose ethers, cellulose esters; for example, natural resinssuch as ethyl cellulose, nitrocellulose, cellulose acetate, andcellulose acetbutyrate; for example, synthetic resins such as rubber androsin resins; for example, polymeric resins and condensation resins; forexample, aminoplast, particularly urea resins, melamine formaldehyderesins, alkyd resins, acrylic resins, polyester or denatured polyester,epoxide, polyisocyanate, or blocked polyisocyanate, polysiloxane, andthe like.

The added amount of other additives is preferably 10 mass % or less andmore preferably 5 wt % or less with respect to 100 mass % of the totalweight of the second barrier layer.

By using the polysilazane coating solution, since there are no cracksand holes, the dense glass-like layer having excellent high barrieraction to gases can be produced.

Subsequently, in the case where the coating solution includes a solvent,it is preferable to dry the solvent in the coating film formed bypolysilazane before being subjected to the conversion treatment. At thistime, the condition for removing water may be adopted. The dryingtemperature is preferably a high temperature from the viewpoint of quicktreatment, but considering the heat damage to the resin film substrate,it is preferable to determine properly the temperature and treatingtime. For example, in the case of using a polyethylene terephthalatesubstrate having a glass transition temperature (Tg) of 70° C. as aplastic substrate, the heat treatment temperature may be set to be 200°C. or lower. The treating time is preferably set to be a short time inorder to remove the solvent and reduce the heat damage to a substrate.When the drying temperature is 200° C. or lower, the treating time maybe set to be 30 minutes or shorter.

It is preferable that for the coating film formed with polysilazane,water be removed before the conversion treatment or during theconversion treatment. For this reason, for preparing the polysilazanelayer, after drying as a purpose of removing the solvent, it ispreferable to include a process (dehumidification treatment) as apurpose of removing water in the coating film. By removing water beforethe conversion treatment or during the conversion treatment, theefficiency of subsequent conversion treatment is improved.

As a method for removing water, it is preferable to use a type of thedehumidification by maintaining the environment of low humidity. Thehumidity in the environment of low humidity changes according to atemperature, and thus, the preferred type of the relation between thetemperature and humidity is exhibited by the determination of adew-point temperature. The preferred dew-point temperature is 4° C.(Temperature of 25° C./Humidity of 25%) or lower, and more preferably−8° C. (Temperature of 25° C./Humidity of 10%) or lower, and it ispreferable to set properly the maintained time by the film thickness ofthe polysilazane layer. For the condition that the film thickness of thepolysilazane layer is 1.0 μm or less, it is preferable that thedew-point temperature be −8° C. or lower and the maintained time thereofbe 5 minutes or longer. In addition, the lower limit of the dew-pointtemperature is not particularly limited, but generally −50° C. orhigher, and preferably −40° C. or higher. In addition, in order toeasily remove water, a reduced pressure drying process may be performed.As the pressure of the reduced pressure drying process, an atmosphericpressure to 0.1 MPa may be selected.

It is preferable that the coating film be subjected to the conversiontreatment while maintaining the state thereof even after removing water.

(Conversion Treatment)

Subsequently, the coating film obtained is subjected to the conversiontreatment. Here, the conversion treatment indicates a conversionreaction of polysilazane into silicon oxide and/or silicon oxynitride.In other words, it is preferable that by performing the conversiontreatment, polysilazane be converted into silica to be SiOxNy. Here, xis preferably 0.5 to 2.3, more preferably 0.5 to 2.0, and still morepreferably 1.2 to 2.0. In addition, y is preferably 0.1 to 3.0, morepreferably 0.15 to 1.5, and still more preferably 0.2 to 1.3.

Here, by silica conversion, Si—H and N—H bond is cleaved and Si—O bondis generated to convert into ceramics such as silica. The degree ofconverting into ceramics may be semi-quantitatively evaluated by thefollowing defined Equation (1) using an IR measurement.

[Mathematical Formula 1]

SiO/SiN ratio=SiO absorbance value after conversion/SiN absorbance valueafter conversion  Equation (1)

Here, the SiO absorbance value and the SiN absorbance value arecalculated by the characteristic absorptions of about 1160 cm⁻¹ andabout 840 cm⁻¹, respectively. As the ratio of SiO/SiN is higher, it isexhibited that the conversion into the ceramics having the compositionthat is close to the silica composition is being progressed.

The ratio of SiO/SiN that is an indicator for the degree of convertinginto ceramics is 0.3 or more, and preferably 0.5 or more. In theserange, the favorable gas barrier performance is obtained.

As a method for measuring the rate of converting into silica (x inSiOx), the rate may be measured by using an XPS method, for example.

The composition of the metal oxide (SiOx) of the second barrier layermay be measured by measuring an atomic composition ratio using an XPSsurface analyzer. In addition, the composition may be also measured bymeasuring an atomic composition ratio, on the cutting section preparedby cutting the gas barrier layer, using an XPS surface analyzer.

A method for preparing a layer by a conversion of polysilazane intosilica is not particularly limited, and examples thereof may include aheat treatment, a plasma treatment, an ozone treatment, an ultravioletrays treatment, and the like. Since the conversion treatment may beeffectively performed at a low temperature in the range that can beapplied on a plastic substrate, it is preferable to perform theconversion treatment by irradiating ultraviolet rays of 400 nm or less,especially, vacuum ultraviolet rays (VUV) of the wavelength of less than180 nm, to the coating film obtained by applying the polysilazanecoating solution. The ozone or active oxygen atom generated byultraviolet rays (synonymous with UV light) has high oxidation abilityand can form a silicon oxide film or silicon oxynitride film having highdense property and insulating property at a low temperature.

By the irradiation of the ultraviolet rays, O₂ and H₂O contributing tobe ceramics, an ultraviolet ray absorbent, and polysilazane itself areexcited and activated. In addition, the excited polysilazane is promotedto be ceramics, and thus, the obtained ceramic film becomes dense. Theirradiation of the ultraviolet rays may be effectively performed even ifit is performed at any points as long as it is performed after forming acoating film.

(Ultraviolet Rays Irradiation Treatment)

As described above, for the conversion treatment, an ultraviolet raysirradiation treatment, especially, a vacuum ultraviolet rays irradiationtreatment is preferably used. Here, it is preferable that at least onekind of the ultraviolet rays of 400 nm or less to be irradiated be avacuum ultraviolet rays irradiation light (VUV) having a wavelengthcomponent of less than 180 nm. At this time, the ultraviolet raysirradiation treatment is preferably performed in the presence of air orozone in order to effectively progress the conversion into silica.

The ultraviolet rays irradiation may be performed one time, or may beperformed two or more times, repeatedly. However, at least one time ofthe ultraviolet rays of 400 nm or less to be irradiated is preferably anultraviolet rays irradiation light (UV) having the wavelength componentof 300 nm or less, especially, a vacuum ultraviolet rays irradiationlight (VUV) having the wavelength component of less than 180 nm.

For example, when the radiation source having a radiation component ofthe wavelength of 300 nm or less such as a Xe₂* excimer radiator havingthe maximum emission of about 172 nm or a low-pressure mercury vaporlamp having an emission line of about 185 nm is used, in the presence ofoxygen and/or water vapor, an ozone and oxygen radical and hydroxylradical are very effectively generated by the photolysis caused by ahigh absorption coefficient of these gases in the wavelength rangedescribed above, and promotes the oxidation of the polysilazane layer.Both mechanisms, that is, the breakage of the Si—N bond and the actionsof the ozone, oxygen radicals, and hydroxyl radicals can be generatedonly after ultraviolet rays reach on the surface of the polysilazanelayer.

For this reason, in order to apply the ultraviolet rays (especially, aVUV radiation) with a dose of radioactivity as high as possible on thesurface of the layer, in some cases, it is necessary for the abovewavelength range that the pass length of the ultraviolet rays is reducedto correspond to the concentrations of the oxygen and water vapor to bedesired by substituting with nitrogen in the passage of the ultravioletrays (especially, a VUV radiation) treatment, and then supplying oxygenand water vapor thereto to be capable of being adjusted.

Here, in the process of irradiating the vacuum ultraviolet rays,estimated mechanism why the coating film including polysilazane isconverted to be SiO_(x)N_(y) will be described with perhydropolysilazaneas an example.

Perhydropolysilazane may be represented as the composition,“—(SiH₂—NH)_(n)—”. In the case where perhydropolysilazane is representedby SiO_(x)N_(y), x=0 and y=1. In order to be x>0, an oxygen source isrequired from the outside. As the oxygen source, the following are used:(i) oxygen or water included in a polysilazane coating solution; (ii)oxygen or water that is taken into the coating film from the atmosphereof the coating drying process; (iii) oxygen or water, ozone, and singletoxygen, which are taken into the coating film from the atmosphere of thevacuum ultraviolet rays irradiation process; (iv) oxygen or water thatis transferred into the coating film as the out gases from the side ofthe substrate by the heat, and the like, applied in the vacuumultraviolet rays irradiation process; and (v) oxygen or water that istaken into the coating film from the atmosphere when a non-oxidativeatmosphere is moved into an oxidative atmosphere in the case where thevacuum ultraviolet rays irradiation process is performed in thenon-oxidative atmosphere.

Meanwhile, it is considered that for y, as compared with the oxidationof Si, the condition in which the nitrification progresses is veryspecific, so that the upper limit thereof is basically 1.

In addition, in the relation of the combining hands of Si, O, and N, xand y are basically in the range of 2x+3y≦4. In the state of y=0 inwhich the oxidation has completely proceeded, a silanol group isincluded in the coating film and the range of 2<x<2.5 may be establishedin some cases.

In the vacuum ultraviolet rays irradiation process, the reactionmechanism estimated that silicon oxynitride and furthermore, siliconoxide is generated from perhydropolysilazane will be describedhereinafter.

(I) Dehydrogenation and Formation of Si—N Bond Therewith

It is considered that a Si—H bond and N—H bond in perhydropolysilazaneare cleaved with relative ease by the excitation due to the vacuumultraviolet rays irradiation, and are recombined as Si—N under the inertatmosphere (a uncombined hand of Si may be formed in some cases). Inother words, it is cured as a SiN_(y) composition without beingoxidized. In this case, the cleavage of a polymer main chain is notgenerated. The cleavage of the Si—H bond or the Ni—H bond is promoted bythe presence of a catalyst or by heating. Cleaved H is released as H₂ tothe outside of a film.

(II) Formation of Si—O—Si Bond by Hydrolysis-Dehydration Condensation

A Si—N bond in perhydropolysilazane is hydrolyzed with water and apolymer main chain is cleaved to form Si—OH. Two Si—OH moieties aresubjected to the dehydration condensation to form a Si—O—Si bond tocause curing. This is a reaction that also occurs in atmospheric air. Itis considered that water vapor generated as an out gas from a substrateby the heat due to irradiation is a major water source during theirradiation with vacuum ultraviolet rays in an inert atmosphere. In thecase of excessive water, Si—OH that cannot be completely subjected todehydrative condensation remains to form a cured film having a low gasbarrier property, represented by composition of SiO 2.3-2.

(III) Direct Oxidation and Formation of Si—O—Si Bond by Singlet Oxygen

When an adequate amount of oxygen exists under an atmosphere duringirradiation with vacuum ultraviolet rays, singlet oxygen with very highoxidizability is formed. H and N in perhydropolysilazane are replaced byO to form a Si—O—Si bond to cause curing. It is considered that bondrearrangement may also be caused by cleaving a polymer main chain insome cases.

(IV) Oxidation with Si—N Bond Cleavage by Irradiation/Excitation withVacuum Ultraviolet Rays

It is considered that, since the energy of vacuum ultraviolet rays ishigher than the bond energy of Si—N in perhydropolysilazane, a Si—N bondis cleaved and oxidized in the presence of an oxygen source such asoxygen, ozone, or water in surroundings to form a Si—O—Si bond or Si—O—Nbond to be formed. It is considered that rearrangement of a bond mayalso be caused by cleaving a polymer main chain in some cases.

The adjustment of the composition of silicon oxynitride of the layer, inwhich the layer including polysilazane is subjected to the vacuumultraviolet irradiation, may be performed by controlling an oxidationstate through properly combining the oxidation mechanism of the above(I) to (IV).

For the excellent barrier action to a gas, especially, water vapor inthe vacuum ultraviolet rays irradiation process, the polysilazane layer(an amorphous polysilazane layer) applied as described above isconverted into a glass-like reticulated structure of silicon dioxide. Bydirectly starting an oxidative conversion of polysilazane frame into athree-dimensional SiO, reticulated structure by a VUV photon, theconversion is performed for a very short time in a single step.

(Vacuum Ultraviolet Rays Irradiation Treatment: Excimer IrradiationTreatment)

The most preferred conversion treatment method is treatment by vacuumultraviolet ray irradiation (excimer irradiation treatment). Thetreatment by the vacuum ultraviolet ray irradiation is a method forforming a silicon oxide film at comparatively low temperature (about200° C. or less) by making an oxidation reaction proceed by activeoxygen or ozone while directly cutting an atomic bond by the action ofonly a photon, called a light quantum process, using the energy of lightof 100 to 200 nm, higher than interatomic bonding force in apolysilazane compound, preferably using the energy of light with awavelength of 100 to 180 nm.

At the time of performing an excimer irradiation treatment, theconversion into silica is promoted, and thus, it is preferable toperform it along with a heat treatment. As a heat treatment, forexample, there may be a method for heating a coating filmby a heatconduction through contacting a substrate with a heating unit such as aheat block, a method for heating the atmosphere by the outside heatersuch as a resistance wire, and a method using a light in an infraredregion such as an IR heater, but the present invention is not limitedthereto. In addition, a method capable of maintaining the smoothness ofa coating film including a silicon compound may be properly selected.

It is preferable that the heating temperature be properly adjusted inthe range of 50° C. to 250° C. In addition, it is preferable that theheating time be in the range of 1 second to 10 hours.

For the irradiation with the vacuum ultraviolet rays, the irradiationstrength and irradiation time are preferably set in the range, in whicha substrate to be irradiated is not damaged.

In the vacuum ultraviolet rays irradiation process, the illumination ofthe vacuum ultraviolet rays on the coating side of the coating film ofthe polysilazane layer is preferably 30 to 200 mW/cm² and morepreferably 50 to 160 mW/cm². In this range, the conversion efficiency isfavorable and also there is minor damage affected to the substrate.

The irradiation energy amount of the vacuum ultraviolet rays on thecoating side of the polysilazane layer is preferably 200 to 5000 mJ/cm²,and more preferably 500 to 3000 mJ/cm². In this range, the modificationefficiency is favorable and also there is minor damage affected to thesubstrate.

As a vacuum ultraviolet light source, a noble gas excimer lamp ispreferably used. A noble gas atom such as Xe, Kr, Ar, or Ne is notchemically bound to make a molecule and is therefore referred to as aninert gas. However, an excited atom of noble gas gaining energy bydischarge and/or the like can be bound to another atom to make amolecule. When the noble gas is xenon,

e+Xe→Xe*

Xe*+2Xe→Xe₂*+Xe

Xe₂*+Xe+Xe+hν(172 nm)

are established, excimer light of 172 nm is emitted when transition ofXe₂*, which is an excited excimer molecule, to a ground state occurs.

Features of the excimer lamp include high efficiency due toconcentration of emission on one wavelength to cause almost no emissionof light other than necessary light. Further, the temperature of anobject can be kept low since surplus light is not emitted. Furthermore,instant lighting and flashing are possible since time is not needed forstarting and restarting.

A method of using dielectric barrier discharge is known to provideexcimer light emission. The dielectric barrier discharge is very thindischarge called micro discharge, like lightning, generated in the gasspace, which is disposed between both electrodes via a dielectric suchas a transparent quartz, by applying a high frequency and a high voltageof several tens of kHz to the electrodes, and, when a streamer of themicro discharge reaches a tube wall (dielectric), a dielectric surfaceis charged, and thus, the micro discharge becomes extinct.

It is discharge in which the micro discharge spreads over the whole tubewall and generation and extinction thereof are repeated. Therefore,light flicker which can be recognized even by naked eyes occurs. Since astreamer at very high temperature reaches directly the tube walllocally, there is also a possibility in that deterioration in the tubewall may be accelerated.

For a method of efficiently obtaining excimer light emission,electrodeless electric field discharge, other than the dielectricbarrier discharge, is also possible. It is electrodeless electric fielddischarge by capacitive coupling and is also sometimes called RFdischarge. Although a lamp, electrodes, and arrangement thereof may bebasically the same as those in the dielectric barrier discharge, a highfrequency applied between both electrodes illuminates at several of MHz.In the electrodeless electric field discharge, discharge uniform interms of space and time is obtained as described above and along-lasting lamp without flicker is therefore obtained.

In the case of the dielectric barrier discharge, since micro dischargeoccurs only between the electrodes, the outside electrode must cover thewhole external surface and have a material, through which light passes,for taking out light to the outside, in order to effect discharge in thewhole discharge space.

Therefore, the electrode in which thin metal wires are reticulated isused. This electrode is easily damaged by ozone, and the like, generatedby vacuum-ultraviolet light in the oxygen atmosphere since wires whichare as thin as possible are used so as not to block light. Forpreventing this, it is necessary to make the periphery of the lamp, thatis, the inside of an irradiation apparatus have inert gas atmospheresuch as nitrogen and to dispose a window with synthetic quartz to takeout irradiated light. The window with synthetic quartz is not only anexpensive expendable product but also causes the loss of light.

Since a double cylinder type lamp has an outer diameter of about 25 mm,a difference between the distances to an irradiated surface just under alamp axis and on the side surface of the lamp is unnegligible to cause asignificant difference in illuminance. Accordingly, even if such lampsare closely arranged, no uniform illumination distribution is obtained.The irradiation apparatus provided with the window with synthetic quartzenables equal distances in the oxygen atmosphere and provides a uniformillumination distribution.

It is not necessary to reticulate an external electrode whenelectrodeless electric field discharge is used. Only by disposing theexternal electrode on a part of the external surface of the lamp, glowdischarge spreads over the whole discharge space. For the externalelectrode, an electrode which serves as a light reflecting platetypically made of an aluminum block is used on the back surface of thelamp. However, since the outer diameter of the lamp is large as in thecase of the dielectric barrier discharge, synthetic quartz is requiredfor making a uniform illumination distribution.

The maximum feature of a narrow tube excimer lamp is a simple structure.Both ends of a quartz tube are only closed to seal a gas for excimerlight emission therein.

The tube of the narrow tube lamp has an outer diameter of about 6 nm to12 mm, and a high voltage is needed for starting when it is too thick.

As discharge form, any of dielectric barrier discharge and electrodelesselectric field discharge can be used. As for the shape of the electrode,a surface contacting with the lamp may be planar; however, the lamp canbe well fixed and the electrode closely contacts with the lamp tostabilize discharge well by the shape fitting with the curved surface ofthe lamp. Further, a light reflecting plate can be also made when thecurved surface is made to be a specular surface with aluminum.

The preferred radiation source is an excimer radiator (for example, a Xeexcimer lamp) having a maximum radiation of about 172 nm, a low-pressuremercury water vapor lamp having the emission line of about 185 nm, anintermediate-pressure and high-pressure mercury water vapor lamp havinga wavelength component of 230 nm or less, and an excimer lamp having amaximum radiation of about 222 nm.

Among them, the Xe excimer lamp is excellent in luminous efficiencysince an ultraviolet ray with a short wavelength of 172 nm is radiatedas a single wavelength. This light enables a high concentration of aradical oxygen atomic species or ozone to be generated with a very smallamount of oxygen because of having a high oxygen absorption coefficient.Further, the energy of light with a short wavelength of 172 nm is knownto have a high capacity of dissociating the bond of organic matter. Theconversion of a polysilazane layer can be realized in a short time bythe high energy of this active oxygen or ozone and ultravioletradiation.

The excimer lamp can be made to illuminate by input of a low powerbecause of having high light generation efficiency. Further, it does notemit light with a long wavelength which becomes a factor for increasingtemperature due to light, but irradiates energy in an ultraviolet range,that is, with a short wavelength, and thus, has the characteristiccapable of suppressing increase in the surface temperature of an articleto be irradiated. Therefore, it is suitable for a flexible film materialsuch as PET, which is considered to be easily subject to heat effect.

Accordingly, shortening of process time and reduction in the area of afacility, caused by a high throughput, and irradiation of an organicmaterial, a plastic substrate, or the like, which is easily damaged byheat, are made to be possible in comparison with the low-pressuremercury lamp which emits wavelengths of 185 nm and 254 nm and the plasmacleaning.

In addition, the action of UV light without including a wavelengthcomponent of 180 nm or less from the low-pressure mercury lamp (a HgLPlamp) (185 nm and 254 nm) which emits the wavelengths of 185 nm and 254nm or a KrCl*excimer lamp (222 nm) is limited to a direct photolysisaction to a Si—N bond, and in other words, an oxygen radical or hydroxylradical is not generated. In this case, since the degree of absorptionis as small as negligible, the limit relating to the concentrations ofoxygen and water vapor is not required. Another advantage of the lighthaving shorter wavelength is that the penetration depth to thepolysilazane layer is bigger.

A reaction during irradiation with ultraviolet rays requires oxygen.Since vacuum ultraviolet rays are easily prone to decrease efficiency inan ultraviolet ray irradiation process due to absorption by oxygen, itis preferable to perform the irradiation with vacuum ultraviolet rays inthe state in which an oxygen concentration and a water vaporconcentration is as low as possible. The oxygen concentration during theirradiation with vacuum ultraviolet rays is preferably 10 to 210,000volume ppm, more preferably 50 to 10,000 volume ppm, and still morepreferably 500 to 5,000 volume ppm. In addition, the water vaporconcentration between the conversion processes is preferably in therange of 1,000 to 4,000 volume ppm.

As a gas filled in an irradiation atmosphere used during the irradiationwith vacuum ultraviolet rays, a dry inert gas is preferred, and a drynitrogen gas is particularly preferred from the viewpoint of a cost. Theadjustment of the oxygen concentration can be performed by measuring theflow rates of an oxygen gas and an inert gas introduced into anirradiation house and changing a flow ratio.

<Substrate>

The materials constituting a substrate is not particularly limited, buta synthetic resin (plastic) is preferable from the viewpoint of weightlightening. The material quality and thickness of the plastic substrateused are not particularly limited as long as the film is capable ofmaintaining a barrier laminate, and the plastic substrate may beproperly selected according to the use purpose, and the like. Specificexamples of the plastic substrate may include thermoplastic resins suchas polyester resins such as polyethylene terephthalate, polybutylenenaphthalate, (PEN) polyethylene terephthalate, and polyethylenenaphthalate (PEN), methacrylic resin, a methacrylate-maleic acidcopolymer, a polystyrene resin, a transparent fluoric resin, polyimide,a fluorination polyimide resin, a polyamide resin, a polyamideimideresin, a polyetherimide resin, a cellulose acylate resin, a polyurethaneresin, a polyetheretherketone resin, a polycarbonate resin, an alicyclicpolyolefin resin, a polyacrylate resin, a polyether sulfone resin, apolysulfone resin, a cycloolefin copolymer, a fluorene ring-modifiedpolycarbonate resin, an alicyclic-modified polycarbonate resin, afluorene ring-modified polyester resin, and a acryloyl compound.

When the gas barrier film of the present invention is used as asubstrate of a device such as an organic EL element to be describedbelow, the plastic substrate is preferably composed of a material havingheat resistance. In detail, it is preferably constituted of atransparent material having a glass transition temperature (Tg) of 100°C. or higher and/or linear thermal expansion coefficient of 40 ppm/° C.or lower, and having high heat resistance. The Tg and linear thermalexpansion coefficient can be adjusted by additives, and the like.Examples of the thermoplastic resin may include polyethylene naphthalate(PEN: 120° C.), polycarbonate (PC: 140° C.), alicyclicpolyolefin (forexample, ZEONOR 1600 prepared by Zeon Corporation.: 160° C.),polyacrylate (PAr: 210° C.), polyether sulfone (PES: 220° C.),polysulfone (PSF: 190° C.), a cycloolefin copolymer (COC: the compounddisclosed in Japanese Patent Application Laid-Open No. 2001-150584: 162°C.), polyimide (for example, Neo Prim prepared by Mitsubishi GasChemical Company, Inc.: 260° C.), fluorene ring-modified polycarbonate(BCF-PC: the compound disclosed in Japanese Patent Application Laid-OpenNo. 2000-227603: 225° C.), alicyclic-modified polycarbonate (IP-PC: thecompound disclosed in Japanese Patent Application Laid-Open No.2000-227603: 205° C.), and an acryloyl compound (the compound disclosedin Japanese Patent Application Laid-Open No. 2002-80616: 300° C. orhigher) (the parenthesis represents Tg). Especially, in the case ofrequiring transparency, the alicyclic polyolefin and the like may bepreferably used.

In the case where the gas barrier film is used in combination with apolarizing plate, it is preferable that the gas barrier unit (laminate)of the gas barrier film be faced at the inside of a cell and be disposedin the innermost (adjacent to the element). At that time, since the gasbarrier film is disposed in the inside of the cell relative to thepolarizing plate, a retardation value of the gas barrier film isimportant. As to a use form of the gas barrier film in such anembodiment, it is preferable that a gas barrier film using a basematerial film having a retardation value of 10 nm or less and a circularpolarizing plate (quarter-wave plate+(half-wave plate)+linear polarizingplate) be laminated and used, or that a linear polarizing plate becombined and used with a gas barrier film using a base material filmhaving a retardation value of from 100 nm to 180 nm, which can be usedas a quarter-wave plate.

Examples of the base material film having a retardation of 10 nm or lessmay include cellulose triacetate (FUJITAC, manufactured by FujifilmCorporation), polycarbonates (PURE-ACE, manufactured by Teijin Limited;and ELMECH, manufactured by Kaneka Corporation), cycloolefin polymers(ARTON, manufactured by JSR Corporation; and ZEONOR, manufactured byZeon Corporation), cycloolefin copolymers (APEL (pellet), manufacturedby Mitsui Chemicals, Inc.; and TOPAS (pellet), manufactured byPolyplastics Co., Ltd.), polyarylates (U100 (pellet), manufactured byUnitika Ltd.) and transparent polyimides (NEOPULIM, manufactured byMitsubishi Gas Chemical Company, Inc.).

In addition, films obtained by properly stretching the foregoing film toadjust it so as to have a desired retardation value can be used as thequarter-wave plate.

The substrate is preferably transparent. This is because when thesubstrate is transparent and the layer formed on the substrate is alsotransparent, it is possible to be a transparent gas barrier film, andthus, it is also possible to be a transparent substrate of an organic ELelement. In detail, the light transmittance of the substrate isgenerally 80% or more, preferably 85% or more, and more preferably 90%or more. The light transmittance can be measured by a method describedin JIS-K7105 (2010), namely by measuring a total light transmittance andan amount of scattered light using an integrating sphere type lighttransmittance analyzer and subtracting the diffuse transmittance fromthe total light transmittance.

Even in the case where the gas barrier film is used for display use, forexample, when it is not disposed on the side of an observer, thetransparency is not always required. Accordingly, in such a case, anopaque material can also be used as the plastic substrate. Examples ofthe opaque material may include known liquid crystal polymers such aspolyimides and polyacrylonitrile.

The thickness of the substrate is properly selected depending upon theuse, and thus, is not particularly limited, however, it is typicallyfrom 1 to 800 μm, and preferably from 10 to 200 μm.

<Other Treatments•Other Layers>

The various known treatments (for example, a corona discharge treatment,a flame treatment, an oxidation treatment, a plasma treatment, an UVtreatment, and a glow discharge treatment) may be performed to improvean adhesive property on both sides of the substrate, at least the sideprovided with the barrier layer, and also, if necessary, another organiclayer (for example, an anchor coat layer, a primer layer, a bleedoutlayer), and functional layers such as a protective layer, an absorptionlayer, and an antistatic layer may be provided. Here, the anchor coatlayer, primer layer, and bleedout preventing layer will be described.

(Anchor Coat Layer)

An anchor coat layer may be formed on the surface of the substrate as aneasy adhesive layer for the purpose of improving an adhesive property (aadhesion property) with the barrier layer. Examples of anchor coatagents used for the anchor coat layer may include polyester resins,isocyanate resins, urethane resins, acrylic resins, ethylene vinylalcohol resins, vinyl modified resins, epoxy resins, modified styreneresins, modified silicone resins, alkyl titanate, and the like, whichcan be used singly or in combination of two or more kinds thereof. Asthe anchor coat agents, products on the market may be used. In detail, asiloxane-based UV-cured polymer solution (3% isopropyl alcohol solutionof “X-12-2400” manufactured by Shin-Etsu Chemical Co., Ltd.) can beused.

In addition, especially in the case where an anchor coat layer is formedas the lower layer at the time of forming a first or third barrier layerby an ALD method, examples of the anchor coat agent may includewater-soluble polymers such as gelatine (derivative), casein, agar, analignate, starch, polyvinyl alcohol, a polyacrylic acid (salt),polymaleic acid (salt), cellulose derivatives such ascarboxymethylcellulose, and hydroxyethyl cellulose; polyvinyl alcohol,and the like.

An additive known in the art can also be added to these anchor coatagents. In addition, a substrate may be coated with the anchor coatagent by the known methods such as a roll coating, a gravure coating, aknife coating, a dip coating, and a spray coating, and be dried toremove a solvent, a diluent, and the like. The applying amount of thecoated anchor coat agent as described above is preferably about 0.1 to 5g/m² (in a dry state). In addition, the substrate attached with an easyadhesive layer that is available on the market may be used.

The thickness of the anchor coat layer is not particularly limited, butpreferably about 0.5 to 10.0 μm.

In addition, the anchor coat layer may be used as the following smoothlayer.

(Primer Layer (Smooth Layer))

The gas barrier film may also include a primer layer (a smooth layer).The primer layer is disposed in order to flatten the roughened surfaceof a transparent resin film substrate, on which projections, and thelike are present, or to fill and flatten recesses and projections orpinholes generated in the transparent first barrier layer by theprojections present on the transparent resin film substrate. Such aprimer layer is basically formed by curing a photosensitive material ora thermosetting material.

Examples of the photosensitive material used for forming the primerlayer may include a resin composition comprising an acrylate compoundhaving a radical reactive unsaturated compound; a resin compositioncomprising an acrylate compound and a mercapto compound having a thiolgroup; a resin composition in which a polyfunctional acrylate monomersuch as epoxy acrylate, urethane acrylate, polyester acrylate, polyetheracrylate, polyethylene glycol acrylate, or glycerol methacrylate isdissolved; and the like. In detail, an UV-cured organic/inorganic hybridhard coat material OPSTAR (Registered trademark) series manufactured byJSR Corporation can be used. In addition, such resin compositions asdescribed above can also be optionally mixed and used, and thephotosensitive material is not particularly limited as long as thematerial is a photosensitive resin containing a reactive monomer havingone or more photopolymerizable unsaturated bonds in a molecule. Inaddition, such resin compositions as described above may also beoptionally mixed and used, and the photosensitive material is notparticularly limited as long as the material is a photosensitive resincontaining a reactive monomer having one or more photopolymerizableunsaturated bonds in a molecule.

Examples of the reactive monomer having one or more photopolymerizableunsaturated bonds in a molecule may include methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexylacrylate, 2-ethyl hexyl acrylate, n-octylacrylate, n-decylacrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzylacrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate,cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethyl hexyl acrylate,glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate,2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate,isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxy ethyl acrylate, stearyl acrylate,ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanedioldiacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate,1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate,2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropyleneglycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate,polyoxyethyl trimethylolpropane triacrylate, pentaerythritoltriacrylate, pentaerythritoltetraacrylate, ethylene oxide modifiedpentaerythritol triacrylate, ethylene oxide modified pentaerythritoltetraacrylate, propione oxide modified pentaerythritol triacrylate,propione oxide modified pentaerythritoltetraacrylate, triethylene glycoldiacrylate, polyoxypropyl trimethylolpropane triacrylate, butyleneglycol diacrylate, 1,2,4-butanediol triacrylate,2,2,4-trimethyl-1,3-pentadiol diacrylate, diallyl fumarate,1,10-decanediol dimethylacrylate, pentaerythritol hexaacrylate, andmonomers obtained by substituting the above-described acrylates bymethacrylates, γ-methacryloxypropyltrimethoxysilane,1-vinyl-2-pyrrolidone, and the like. The above-described reactivemonomers may be used singly or as mixtures of two or more kinds thereofor as mixtures with other compounds.

A composition of the photosensitive resin includes a photopolymerizationinitiator.

Examples of the photopolymerization initiator may include benzophenone,o-benzoylmethyl benzoate, 4,4-bis(dimethylamine)benzophenone,4,4-bis(diethylamine)benzophenone, α-amino.acetophenone,4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzylketone, fluorenone, 2,2 diethoxyacetophenone,2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone,p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone,2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,benzyldimethyl ketal, benzyl methoxyethyl acetal, benzoin methyl ether,benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone,2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone,dibenzosuberone, methyleneanthrone, 4-azidobenzylacetophenone,2,6-bis(p-azidobenzylidene)cyclohexane,2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone,2-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime,1-phenyl-propanedione-2-(o-ethoxycarbonyl)oxime,1,3-diphenyl-propanetrione-2-(o-ethoxycarbonyl)oxime,1-phenyl-3-ethoxy-propanetrione-2-(o-benzoyl)oxime, Michler's ketone,2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propane,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,naphthalenesulfonyl chloride, quinoline sulfonyl chloride,n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide,benzthiazole disulfide, triphenylphosphine, camphorquinone, carbontetrabromide, tribromophenylsulfone, benzoin peroxide, and eosine, aswell as combinations of a photoreductive pigment such as Methylene Blueand a reducing agent such as ascorbic acid or triethanolamine, and thelike. These photopolymerization initiators may be used singly or incombination of two or more kinds thereof.

Specific examples of the thermosetting material may include tutoPromseries (organic polysilazane) manufactured by Clariant, SP COATheat-resistant clear coating material manufactured by Ceramic Coat Co.,Ltd., nanohybrid silicone manufactured by ADEKA Corporation, UNIDIC(Registered trademark) V-8000 Series and EPICLON (Registered trademark)EXA-4710 (super-high-heat-resistant epoxy resin), manufactured by DICCorporation, various silicone resins X-12-2400 (Product name)manufactured by Shin-Etsu Chemical Co., Ltd., inorganic•organicnanocomposite material SSG coat manufactured by Nitto Boseki Co., Ltd.,thermosetting urethane resins comprising acrylic polyols and isocyanateprepolymers, phenol resins, urea melamine resins, epoxy resins,unsaturated polyester resins, silicone resins, and the like. Among them,epoxy resin-based materials having heat resistance are particularlypreferred.

The method for forming a primer layer is not particularly limited, butthe formation is preferably performed by wet coating methods such asspin coating methods, spray methods, blade coating methods, and dipmethods, and dry coating methods such as vapor deposition methods.

In the formation of the primer layer, an additive such as an oxidationinhibitor, an ultraviolet ray absorbing agent, or a plasticizer may beadded to the above-mentioned photosensitive resin, if necessary. A resinor an additive suitable for improving the film forming property or forpreventing occurrence of pinholes on the film may also be used in anyprimer layer irrespective of the lamination position of the primerlayer.

The solvent used for forming a primer layer using a coating solutionprepared by dissolving or dispersing a photosensitive resin in a solventmay be alcohols such as methanol, ethanol, n-propanol, isopropanol,ethylene glycol, and propylene glycol, terpenes such as α- orβ-terpineol, ketones such as acetone, methyl ethyl ketone,cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, and4-heptanone, aromatic hydrocarbons such as toluene, xylene, andtetramethyl benzene, glycol ethers such as cellosolve, methylcellosolve,ethylcellosolve, carbitol, methyl carbitol, ethyl carbitol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol monoethylether, dipropylene glycol monomethyl ether, dipropylene glycol monoethylether, triethylene glycol monomethyl ether, and triethylene glycolmonoethyl ethers, ester acetates such as ethyl acetate, butyl acetate,cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate,carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethylacetate, and 3-methoxybutyl acetate, diethylene glycol dialkyl ether,dipropylene glycol dialkyl ether, 3-ethoxy ethyl propionate, methylbenzoate, N,N-dimethyl acetamide, N,N-dimethylformamide, and the like.

The smoothness of the primer layer is a value represented by the surfaceroughness specified in JIS B 0601:2001, and a maximum cross-sectionalheight Rt(p) is preferably 10 nm or more and 30 nm or less.

The surface roughness is calculated by the section curve of theirregularity that is continuously measured with a detector having thestylus probe of micro tip radius consecutively in AFM (atomic forcemicroscope). By the stylus probe of micro tip radius, many measurementsare performed in the sections of the tens of μm as a measuring directionto obtain the roughness relating to the fine amplitude of theirregularity.

The thickness of the primer layer is not particularly limited, butpreferably in the range of 0.5 to 10 μm.

(Bleedout Preventing Layer)

The gas barrier film may also have a bleedout preventing layer. Thebleedout preventing layer is disposed on the surface opposite to thesurface of the substrate having the smooth layer for the purpose ofinhibiting the phenomenon of the contamination of the contact surfacedue to the migration of an unreacted oligomer, and the like, from thesubstrate of the film to the surface, when the film having the smoothlayer is heated. As long as the bleedout preventing layer has thisfunction, the bleedout preventing layer may basically have the sameconstitution as that of the smooth layer.

As an unsaturated organic compound having a polymerizable unsaturatedgroup, which can be incorporated in the bleedout preventing layer,examples thereof may include a polyvalent unsaturated organic compoundhaving two or more polymerizable unsaturated groups in the molecule or amonovalent unsaturated organic compound having one polymerizableunsaturated group in the molecule.

Here, examples of the polyvalent unsaturated organic compound mayinclude ethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,neopentylglycol di(meth)acrylate, trimethylol propane tri(meth)acrylate,dicyclopentanyl di(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, dipentaerythritolhexa(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate,ditrimethylol propane tetra(meth)acrylate, diethylene glycoldi(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and thelike.

In addition, examples of the monovalent unsaturated organic compound mayinclude methyl (meth)acrylate, ethyl (meth)acrylate,propyl(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl(meth)acrylate,isodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate,allyl(meth)acrylate, cyclohexyl(meth)acrylate, methylcyclohexyl(meth)acrylate, isobornyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol(meth)acrylate,glycidyl(meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, butoxyethyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxydiethyleneglycol(meth)acrylate, methoxy triethylene glycol(meth)acrylate,methoxypolyethylene glycol(meth)acrylate, 2-methoxypropyl(meth)acrylate,methoxy dipropylene glycol(meth)acrylate, methoxy tripropyleneglycol(meth)acrylate, methoxypolypropylene glycol(meth)acrylate,polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acrylate,and the like.

As other additive agents, a matting agent may be included. As a mattingagent, the inorganic particles having an average particle diameter ofabout 0.1 to 5 μm are preferred.

As such inorganic particles, one kind or two or more kinds incombination of silica, alumina, talc, clay, calcium carbonate, magnesiumcarbonate, barium sulfate, aluminum hydroxide, titanium dioxide,zirconium oxide, and the like may be used.

Here, the matting agent that is composed of the inorganic particles isdesirably mixed in the ratio of 2 parts by weight or more, preferably 4parts by weight or more, and more preferably 6 parts by weight or more,but 20 parts by weight or less, preferably 18 parts by weight or less,and more preferably 16 parts by weight or less, with respect to 100parts by weight of the solid content of a hard coat agent.

In addition, in the bleedout preventing layer, a thermoplastic resin, athermosetting resin, an ionizing radiation curable resin, aphotopolymerizable initiator, or the like, as another component exceptthe hard coat agent and the matting agent, may also be included.

As the above-described thermoplastic resin, there may be cellulosederivatives such as acetylcellulose, nitrocellulose, acetyl butylcellulose, ethyl cellulose, and methylcellulose, vinyl-based resins suchas vinyl acetate and a copolymer thereof, vinyl chloride and a copolymerthereof, and vinylidene chloride and a copolymer thereof, acetal-basedresins such as polyvinyl formal, and polyvinyl butyral, acrylic-basedresins such as acrylic resin and a copolymer thereof, and a methacrylicresin and a copolymer thereof, polystyrene resins, polyamide resins,linear polyester resins, polycarbonate resins, and the like.

In addition, examples of the thermosetting resin may include athermosetting urethane resin that is composed of acrylic polyol andisocyanate prepolymers, a phenolic resin, an urea melamine resin, anepoxy resin, an unsaturated polyester resin, a silicone resin, and thelike.

In addition, as the ionizing radiation curable resin, the resin cured byirradiating the ionizing radiation (ultraviolet rays or electron beam)to the ionizing radiation curable coating materials prepared by mixingone kind or two or more kinds of the photopolymerizable prepolymers orphotopolymerizable monomers may be used. Here, as the photopolymerizableprepolymer, it is preferable that the acrylic-based prepolymer having athree-dimensional mesh structure generated by having two or more of theacryloyl groups in one molecule and cross-linking be especially used. Asthe acrylic-based prepolymer, urethane acrylate, polyester acrylate,epoxy acrylate, melamine arylate, and the like may be used. In addition,as the photopolymerizable monomer, the above-described polyvalentunsaturated organic compounds, and the like may be used.

In addition, examples of the photopolymerizable initiator may includeacetophenone, benzophenone, Michler's ketone, benzoin, benzyl methylketal, benzoin benzoate, hydroxy cyclohexyl phenyl ketone,2-methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propane, α-acyloxime ester, thioxanthones, and the like.

The bleedout preventing layer as described above can be formed bypreparing a coating solution by blending a hard coat agent, a mattingagent, and if necessary another component with an diluting solvent whichis appropriately optionally used, coating the coating solution on thesurface of the substrate film by a coating method known in the art, andthen, irradiating the solution with ionizing radiation to cure thesolution. In addition, a method for irradiation with ionizing radiationcan be performed by irradiation with ultraviolet rays in a wavelengthregion of 100 to 400 nm, preferably 200 to 400 nm, emitted from anultra-high-pressure mercury lamp, a high pressure mercury lamp, alow-pressure mercury lamp, a carbon arc, a metal halide lamp, or thelike, or by irradiation with electron beams in a wavelength region of100 nm or less, emitted from a scanning- or curtain-type electron beamaccelerator.

The thickness of a bleedout preventing layer is 1 to 10 μm andpreferably 2 to 7 μm. By being to be 1 μm or more, it is easy that heatresistance as a film is to be sufficient, and by being to be 10 μm orless, it is easy to adjust the balance in the optical properties of thesmooth film and also prevent the curl of the barrier film in the case ofproviding the smooth layer on one side of the transparent polymer film.

In addition to the above-described films, as the gas barrier film of thepresent invention, the films disclosed on Paragraphs [0036] to [0038] ofJapanese Patent Application Laid-Open No. 2006-289627 may be preferablyemployed.

<Electronic Device>

The gas barrier film can be preferably applied to the device, in whichthe performance thereof is deteriorated by the chemical components inthe air (oxygen, water, nitrogen oxide, sulfur oxide, ozone, and thelike). Examples of the above devices may include an electronic devicesuch as an organic EL element, a liquid crystal display device, a thinfilm transistor, a touch panel, an electronic paper, a solar cell, andthe like, and the gas barrier film is preferably used for an organic ELelement.

The gas barrier film may be also used for a film sealing of a device. Inother words, this is a method in that the device itself is used as asupport, and the gas barrier film of the present invention is providedon the surface thereof. Before providing the gas barrier film, thedevice may be covered with a protecting layer.

The gas barrier film of the present invention may be used as a substrateof a device or a film for sealing by a solid sealing method. The solidsealing method is a method comprising forming a protecting layer on adevice, overlapping an adhesive layer and the gas barrier film, andcuring them. An adhesive is not particularly limited, but examplesthereof may include a thermosetting epoxy resin, a photosetting acrylateresin, and the like.

(Organic EL Element)

Examples of the organic EL element using the gas barrier film aredisclosed in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid Crystal Display Element)

The reflection type liquid crystal display device is configured toinclude a lower substrate, a reflection electrode, a lower alignmentfilm, a liquid crystal layer, an upper alignment film, a transparentelectrode, an upper substrate, a λ/4 plate and a polarizing film inorder from the lower side. The gas barrier film of the present inventioncan be used as the transparent electrode substrate and the uppersubstrate. In the case of giving a color displaying function to thereflection type liquid crystal display device, it is preferable tofurther provide a color filter layer between the reflection electrodeand the lower alignment film or between the upper alignment film and thetransparent electrode. Also, the transmission type liquid crystaldisplay device is configured to include a backlight, a polarizing plate,a λ/4 plate, a lower transparent electrode, a lower alignment film, aliquid crystal layer, an upper alignment film, an upper transparentelectrode, an upper substrate, a λ/4 plate and a polarizing film inorder from the lower side. In the case of giving a color displayingfunction to the transmission type liquid crystal display device, it ispreferable to further provide a color filter layer between the lowertransparent electrode and the lower alignment film or between the upperalignment film and the upper transparent electrode. A kind of the liquidcrystal cell is not particularly limited, but it is more preferably a TN(Twisted Nematic) type, an STN (Super Twisted Nematic) type, an HAN(Hybrid Aligned Nematic) type, a VA (Vertically Alignment) type, an ECB(Electrically Controlled Birefringence) type, an OCB (OpticallyCompensated Bend) type, an IPS (In-Plane Switching) type, or a CPA(Continuous Pinwheel Alignment) type.

(Solar Cell)

The gas barrier film of the present invention may be also used as asealing film of a solar cell element. Here, the gas barrier film of thepresent invention preferably seals such that an adhesive layer is to bea close side to the solar cell element. The solar cell element thatpreferably uses the gas barrier film of the present invention is notparticularly limited, but examples thereof may include a single crystalsilicon-based solar cell element, a polycrystalline silicon-based solarcell element, an amorphous silicon-based solar cell element that isconfigured of a single mating type or a tandem structure type, asemiconductor solar cell element of III-V group compounds such asgallium arsenide (GaAs) or indium phosphorus (InP), a semiconductorsolar cell element of II-VI group compounds such as cadmium tellurium(CdTe), a semiconductor solar cell element of I-III-VI group compoundssuch as copper/indium/selenium system (so-called CIS system),copper/indium/gallium/selenium system (so-called CIGS system), orcopper/indium/gallium/selenium/sulfur system (so-called CIGSS system), adye-sensitized solar cell element, an organic solar cell element, andthe like. Among them, in the present invention, the solar cell elementis preferably a semiconductor solar cell element of I-III-VI groupcompounds such as copper/indium/selenium system (so-called CIS system),copper/indium/gallium/selenium system (so-called CIGS system), orcopper/indium/gallium/selenium/sulfur system (so-called CIGSS system).

(Others)

As other application examples, there are a thin film transistordisclosed in Japanese Patent Application National Publication(Laid-Open) No. 10-512104, a touch panel disclosed in Japanese PatentApplication Laid-Open No. 5-127822 or Japanese Patent ApplicationLaid-Open No. 2002-48913, an electronic paper disclosed in JapanesePatent Application Laid-Open No. 2000-98326, and the like.

(Optical Members)

The gas barrier film of the present invention may be used as an opticalmember. Examples of the optical members may include a circularlypolarizing plate, and the like.

(Circularly Polarizing Plate)

The circularly polarizing plate can be prepared by laminating a λ/4plate and a polarizing plate on the gas barrier film of the presentinvention as a substrate. In that case, the both plates are laminated insuch a manner that a slow axis of the λ/4 plate and an absorption axisof the polarizing plate form an angle of 45°. As such a polarizingplate, one stretched in a direction of 45° against the machine direction(MD) thereof is preferably used, and those described in, for example,Japanese Patent Application Laid-Open No. 2002-865554 may be favorablyused.

<Respective Characteristic Values of Gas Barrier Film>

The respective characteristic values of the gas barrier film of thepresent invention may be measured by using the following methods.

(Measurement of Water Vapor Permeability)

Various methods for measuring water vapor permeability according to a Bmethod disclosed in JIS K 7129 (1992) have been proposed. Examplesthereof may representatively include a cup method, a dryness andmoisture sensor method (Lassy method), and an infrared sensor method(mocon method). However, as a gas barrier property is improved, theremay be a measurement limit by these methods, and thus, the followingmethods have been proposed.

(Measuring Method of Water Vapor Permeability in Addition to the AboveMethod)

1. Ca Method

A metal Ca was vapor-deposited on the gas barrier film, and thecorrosion phenomenon of the metal Ca is used with the water permeatingthrough the film. The water vapor permeability is calculated with thecorrosion area and the time for reaching there.

2. Method Suggested by MORESCO Co., Ltd. (Dec. 8, 2009, News Release)

A method for delivering through a cooling trap of water vapor betweenthe sample space under the atmosphere pressure and the mass spectrometerin ultra-high vacuum.

3. HTO Method (US General Atomics Co., Ltd.)

A method for calculating water vapor permeability using tritium.

4. Method Suggested by A-Star (Singapore) (International PatentPublication No. 2005/95924)

A method for calculating water vapor permeability with electricalresistance changes and fluctuation components included therein for thematerials (for example, Ca and Mg), in which the electrical resistancethereof is changed by water vapor or oxygen, using a sensor.

For the gas barrier film of the present invention, the method formeasuring water vapor permeability is not particularly limited, but inthe present specification, as the method for measuring water vaporpermeability, the measurement is performed by the above-described Camethod, and then, the value obtained by performing the above method isdefined to be water vapor permeability (g/m²·24 h).

The water vapor permeability of the gas barrier film of the presentinvention is preferably low, preferably 1×10⁻⁷ to 5×10⁻² g/m²·24 h, andmore preferably, 1×10⁻⁶ to 1×10⁻² g/m²·24 h. In addition, for the gasbarrier film of the present invention, the method for measuring watervapor permeability is not particularly limited, but the water vaporpermeability is represented by a value measured by the above-describedCa method.

(Measurement of Oxygen Permeability)

The oxygen permeability was measured based on the B method (Isopiesticpressure method) disclosed in JIS K7126 (1987) using an oxygenpermeability measuring apparatus (Apparatus name, “OXTRAN” (Registeredtrademark) (“OXTRAN” 2/20) manufactured by MOCON, Inc. USA. in thecondition of a temperature of 23° C. and a humidity of 0% RH. Inaddition, the measurement to two test members was performed one time foreach, and the average value of two measuring values was defined as thevalue of the oxygen permeability.

The oxygen permeability of the gas barrier film of the present inventionis preferably low, but for example, preferably 0.01 g/m²·24 h·atm orless, more preferably 0.001 g/m²·24 h·atm or less, and still morepreferably, less than 0.001 g/m²·24 h·atm (less than detection limit).

EXAMPLES

The effect of the present invention will be described with reference tothe following Examples and Comparative Examples. However, the technicalrange of the present invention is not limited to the following Examples.

The respective characteristic values of the gas barrier film weremeasured by using the following methods.

<<Evaluation of Gas Barrier Film>>

[Measurements of x and y in SiOxN_(y)] The gas barrier layer of each ofthe gas barrier films was measured by an XPS method. In detail, x and yin SiOxN_(y) were calculated by measuring Mg as X-rays anode and 600 Woutput (Acceleration voltage of 15 kV and emission electric current of40 mA) using ESCALAB-200R manufactured by VG Scientific Co. Ltd.

(Evaluation of Water Vapor Barrier Property)

According to the following measuring method, the permeable water amountsof each of the gas barrier films were measured, and then, the watervapor barrier properties were evaluated according to the followingstandards.

(Apparatus)

Vapor deposition device: Vacuum vapor deposition device, JEE-400,manufactured by JEOL, Ltd.

Isothermal-isohumidity oven: Yamato Humidic Chamber IG47M

Metal that is corroded by reacting with water: Calcium

(Particle Materials)

Water vapor-nonpermeable metal: aluminum (φ3 to 5 mm, particlematerials)

(Preparation of Cell for Evaluating Water Vapor Barrier Property)

On the side of the gas barrier layer of the sample, metal calcium wasvapor-deposited by masking the parts other than the parts of the gasbarrier film sample (nine parts of 12 mm×12 mm) to be desirablyvapor-deposited before adhering a transparent conductive film using avacuum vapor deposition device (a vacuum vapor deposition device,JEE-400, manufactured by JEOL Ltd). Then, the mask was removed in avacuum state as it was to vapor-deposit aluminum from another metaldeposition source on the whole surface of one side of the sheet. Afterthe aluminum sealing, the vacuum state was removed, and then quickly,ultraviolet rays were irradiated on a quartz glass having a thickness of0.2 mm through the ultraviolet rays curing resin for sealing(manufactured by Nagase ChemteX Corporation) to be faced to the aluminumsealing side under a dry nitrogen gas atmosphere to prepare a cell forbeing evaluated. In addition, in order to confirm the change of the gasbarrier properties before and after bending, for the gas barrier filmwithout being subjected to a bending treatment and the gas barrier filmtreated by the following bending treatment, similarly, the cells forevaluating the water vapor barrier property were prepared.

The samples, in which the obtained both sides were sealed, were storedunder the high-temperature and high-humidity of 60° C. and 90% RH, andthe amount of the water that was transmitted into a cell was calculatedby using a corrosion amount of a metal calcium based on the methoddisclosed in Japanese Patent Application Laid-Open No. 2005-283561.

In addition, in order to confirm that there is not transmission of thewater vapor from any sides other than the sides of the gas barrierfilms, as a comparison sample, the sample deposited with a metal calciumusing a quartz glass plate having a thickness of 0.2 mm instead of thegas barrier film sample was stored in the same conditions of thehigh-temperature and high-humidity of 60° C. and 90% RH, and then, afterpassing 1000 hours, it was confirmed that there are no calciumcorrosions.

The permeated water amount (g/m²·24 h; WVTR) of each of the gas barrierfilms measured as described above was evaluated.

(Evaluation of Bending Resistance)

For each of the gas barrier films, 100 times of bending at an angle of180° were repeated so as to be the radius having a curvature of 10 mm,and then, the permeated water amount was measured in the same method asdescribed above. Then, with the change of the permeated water amountsbefore and after the bending treatment, the deterioration resistancerate was measured by the following equation, and then, the bendingresistance was evaluated according to the following criteria.

Deterioration resistance rate=(permeated water amount after bendingtest/permeated water amount before bending test)×100(%)

Rank of Bending Property

5: Deterioration resistance rate of 90% or more

4: Deterioration resistance rate of 80% or more and less than 90%

3: Deterioration resistance rate of 60% or more and less than 80%

2: Deterioration resistance rate of 30% or more and less than 60%

1: Deterioration resistance rate of less than 30%

[Measurement of Visible Transmittance: Transparency]

The average transmittance (%) of the visible light (400 to 720 nm) foreach of the gas barrier films was measured by using a spectrophotometerV-570 (manufactured by JASCO Corporation).

Examples 1 and 2 and Comparative Examples 1 to 3 Example 1 Preparationof Gas Barrier Film A-1

(Formation of Anchor Coat Layer)

A corona discharge treatment, an UV radiation treatment, and further aglow discharge treatment were performed on both sides of the substratefilm (cutting polyethersulfone film (a PES film, a thickness of 188 μm,Product Name: SUMIKA Excel 4101GL30, manufactured by SUMITOMO CHEMICALCo., Ltd) in a 20 cm square), and then, the lower coating solution of0.1 g/m² of gelatin, 0.01 g/m² of α-sulfodi-2-ethylhexylsuccinic acidsodium, 0.04 g/m² of salicyclic acid, 0.2 g/m² of p-chlorophenol, 0.012g/m² of (CH₂═CHSO₂CH₂CH₂NHCO)₂CH₂, and 0.02 g/m² ofpolyamide-epichlorohydrin polycondensate was applied on one side (usinga bar coater of 10 mL/m²) to provide an anchor coat layer. The dryingwas performed at 115° C. for 6 minutes (all of the roller or transportsystem or in the drying zone were to be 115° C.).

(Formation of First Barrier Layer)

(Formation of Inorganic Barrier Layer by ALD Method)

A thin film of Al₂O₃ was deposited with an ALD reactor, F-120 model,manufactured by ASM Microchemistry Oy in Finland. Trimethyl aluminum(TMA) and water were used as an aluminum source and an oxygen source,respectively.

A substrate film applied with an anchor coat layer was installed in thereactor to be the anchor coat layer as the top surface, and then thereactor was vacuumed by pulling the reactor with a vacuum pump.Subsequently, a nitrogen gas was purged to adjust the pressure in thereactor to be about 600 to 800 Pa, and next, the temperature in thereactor was heated to be 230° C. Subsequently, the raw materials in apulse phase were introduced in the reactor in the following cycle. Thepulse cycles were TMA: 0.5 second, a nitrogen purge: 1.0 second, water:0.4 second, and a nitrogen purge: 1.5 seconds. At this time, thedeposition rate of Al₂O₃ in TMA and water was 0.07 nm/cycle. Here, thethin film of Al₂O₃ having a thickness of 70 nm was provided byperforming 1000 cycles.

(Formation of Second Barrier Layer)

10 mass % of the dibutyl ether solution of perhydropolysilazane(AQUAMICA NN120-10, a noncatalytic type, manufactured by AZ ElectronicMaterials) was used as a polysilazane coating solution.

The polysilazane coating solution was applied on a first barrier layerso as to be a (average) film thickness of 300 nm after drying by awireless bar, and then dried by treating under the atmosphere of atemperature of 85° C. and a humidity of 55% RH for 1 minute. Then, itwas maintained under the atmosphere of a temperature of 25° C. and ahumidity of 10% RH (a dew-point temperature of −8° C.) for 10 minutes,and then, was subjected to a dehumification treatment to form a coatingfilm.

(Conversion Treatment of Coating Film into Silica by Ultraviolet Light)

Subsequently, the above coating film formed was subjected to aconversion treatment into silica under the condition of a dew-pointtemperature of −8° C. or lower by the following method to form apolysilazane layer (a second barrier layer).

<Ultraviolet Rays Irradiation Apparatus>

Apparatus: Excimer irradiation apparatus, MODEL: MECL-M-1-200,manufactured by M.D.COM, Inc.

Irradiation wavelength: 172 nm

Lamp filler gas: Xe

<Conversion Treatment Condition>

The conversion treatment was performed to the substrate having apolysilazane layer fixed on an operation stage under the followingconditions to form a gas barrier layer.

Excimer Lamplight intensity: 130 mW/cm² (172 nm)

Distance between sample and light source: 1 mm

Stage heating temperature: 70° C.

Oxygen concentration in irradiation apparatus: 1.0%

Excimer lamp irradiation time: 5 seconds

(Formation of Third Barrier Layer)

Subsequently, a thin film of Al₂O₃ by the ALD method was formed on thepolysilazane layer in the same condition as the formation of the firstbarrier layer to obtain the gas barrier film A-1 of Example 1, which hasa three-layer lamination structure of an inorganic barrier layer (afirst barrier layer)/a polysilazane layer (a second barrier layer)/aninorganic barrier layer (a third barrier layer).

Example 2 Formation of Gas Barrier Film A-2

A polysilazane layer and a third barrier layer were further formed onthe gas barrier film A-1 in the same method as the formation method ofthe gas barrier film A-1 to obtain the gas barrier film A-2 of Example2, which has the constitution of an inorganic barrier layer (the firstbarrier layer of the first gas barrier unit)/a polysilazane layer (thesecond barrier layer of the first gas barrier unit)/an inorganic barrierlayer (the third barrier layer of the first gas barrier unit and thefirst barrier layer of the second gas barrier unit)/a polysilazane layer(the second barrier layer of the second gas barrier unit)/an inorganicbarrier layer (the third barrier layer of the second gas barrier unit).

Comparative Example 1 Formation of Gas Barrier Film A-11

A gas barrier film A-11 of Comparative Example 1 was formed in the samemethod as the gas barrier film A-1, except that instead of the formationof the polysilazane layer, a silicon oxide film (a film thickness of 300nm) formed by a general plasma CVD (PECVD) was formed on the firstbarrier layer.

Comparative Example 2 Formation of Gas Barrier Film A-12

A gas barrier film A-12 of Comparative Example 2 was formed in the samemethod as the gas barrier film A-1, except that instead of the layerformed with polysilazane, an organic layer was formed on the firstbarrier layer in the following method.

An acrylic monomer mixture of 50.75 mL of tetraethyleneglycoldiacrylate, 14.5 mL of tripropylene glycolmonoacrylate, 7.25 mL ofcaprolactone acrylate, 10.15 mL of acrylic acid, and 10.15 mL of SarCure(benzophenone mixture photopolymerizable initiator manufactured bySartomer) was mixed with 36.25 gm of solidN,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine particles and then themixture thus obtained was stirred for about 1 hour with a 20 kHzultrasonic wave tissue blender. The mixture was heated at about 45° C.,and the stirred mixture in order to prevent the sedimentation wastransferred by a pump into a 1.3 mm spray nozzle through a capillaryhaving an inside diameter of 2.0 mm and a length of 61 mm, and then,sprayed in a small drop through a 25 kHz ultrasonic waves sprayer, andthus dropped on the surface maintaining about 340° C. The steam wascryo-condensed on the plastic substrate that was the same as Example 1that came in contact with a low temperature drum having a temperature ofabout 13° C., and then, cured with UV by a high pressure mercury vaporlamp (the estimated irradiation amount of about 2000 mJ/cm²) to form anorganic layer. The film thickness thereof was about 300 nm.

Comparative Example 3 Formation of Gas Barrier Film A-13

A gas barrier film A-13 of Comparative Example 3 was formed in the samemethod as the gas barrier film A-1, except that the third barrier layerwas not formed.

For the gas barrier films A-1 and A-2, and the gas barrier films A-11and A-12 for comparisons, the layer configurations other than thesubstrates are listed in the following Table 1.

TABLE 1 No. Layer configuration (layer film thickness in parenthesis)A-1 Al₂O₃ film (70 nm)/polysilazane layer (300 nm)/Al₂O₃ film (70 nm)A-2 Al₂O₃ film (70 nm)/polysilazane layer (300 nm)/Al₂O₃ film (70nm)/polysilazane layer (300 nm)/Al₂O₃ film (70 nm) A-11 Al₂O₃ film (70nm)/silicon oxide film (300 nm)/Al₂O₃ film (70 nm) A-12 Al₂O₃ film (70nm)/organic layer (300 nm)/Al₂O₃ film (70 nm) A-13 Al₂O₃ film (70nm)/polysilazane layer (300 nm)

(Test and Evaluation)

For the gas barrier films A-1 and A-2, and the gas barrier films A-11and A-12 for comparisons, the gas barrier properties were evaluated. Theresults are listed in Table 2.

TABLE 2 Conversion condition of polysilazane coating film HeatingIrradiation Rank of temperature time WVTR Bending Transparency No. (°C.) (seconds) g/m² · 24 h property (%) A-1 70 5 0.001 4 93 Example A-270 5 0.0005 5 92 Example A-11 — — 0.02 2 82 Comparative Example A-12 — —0.03 2 81 Comparative Example A-13 70 5 0.05 1 92 Comparative Example

From the results listed in Table 2, it can be confirmed that as comparedwith the gas barrier films A-11, A-12, and A-13 for comparisons, the gasbarrier films A-1 and A-2 have favorable gas barrier properties (WVTR),bending resistances (bending properties), and high visible lighttransmittance.

Examples 3 and 4 and Comparative Examples 4 to 6

A gas barrier film B-1 of Example 3, a gas barrier film B-2 of Example4, a gas barrier film B-11 of Comparative Example 4, a gas barrier filmB-12 of Comparative Example 5, and a gas barrier film B-13 ofComparative Example 6 were formed in the same methods as Example 1,Example 2, Comparative Example 1, Comparative Example 2, and ComparativeExample 3, respectively, except that the plastic base materials andinorganic layers were formed in the following methods.

In addition, for the following Examples and Comparative Examples, thesame number next to alphabet-exhibits the gas barrier films that areprepared in the same conditions thereof except the specific conditionsdescribed.

The barrier layers were formed on the smoothing surface sides of apolyethylene naphthalate film (a PEN film, a thickness of 100 μm,Product Name: Teonex Q65FA manufactured by Teijin DuPont Films JapanLimited) along the following method, and then were evaluated.

The splice roll was loaded in a roll-to-roll sputter coater. Thepressure in the film formation chamber was reduced by a pump to be2×10⁻⁶ Torr. The gas mixture including 51 sccm of argon and 30 scorn ofoxygen in 2 kW, 600 V, and 1 millitorr pressure and a Si—Al (95/5)target (available from Academy Precision Materials as a product on themarket) using a web rate of 0.43 m/min were reactive-sputtered todeposit a SiAlO inorganic oxide layer (a first barrier layer) having athickness of 60 nm on a substrate film. Similarly, the third barrierlayer was formed on the second barrier layer.

For the gas barrier films B-1 and B-2, and the gas barrier films B-11and B-12 for comparisons, the layer configurations other than thesubstrates are listed in the following Table 3. In addition, the resultsof evaluating the gas barrier properties are listed in Table 4.

TABLE 3 No. Layer configuration (layer film thickness in parenthesis)B-1 SiAlO film (60 nm)/polysilazane layer (300 nm)/SiAlO film (60 nm)B-2 SiAlO film (60 nm)/polysilazane layer (300 nm)/SiAlO film (60nm)/polysilazane layer (300 nm)/SiAlO film (60 nm) B-11 SiAlO film (60nm)/silicon oxide film (300 nm)/SiAlO film (60 nm) B-12 SiAlO film (60nm)/organic layer (300 nm)/SiAlO film (60 nm) B-13 SiAlO film (60nm)/polysilazane layer (300 nm)

TABLE 4 Conversion condition of polysilazane coating film HeatingIrradiation Rank of No. temperature time WVTR Bending Transparency No.(° C.) (seconds) g/m₂ · 24 h property (%) B-1 70 5 0.002 4 91 ExampleB-2 70 5 0.008 5 90 Example B-11 — — 0.01 2 80 Comparative Example B-12— — 0.02 2 81 Comparative Example B-13 70 5 0.06 2 95 ComparativeExample

From the results listed in Table 4, it can be confirmed that as comparedwith the gas barrier films B-11, B-12, and B-13 for comparisons, the gasbarrier films B-1 and B-2 have favorable gas barrier properties (WVTR),bending resistances (bending properties), and high visible lighttransmittance.

Examples 5 and 6 and Comparative Examples 7 to 9

A gas barrier film C-1 of Example 5, a gas barrier film C-2 of Example6, a gas barrier film C-11 of Comparative Example 6, a gas barrier filmC-12 of Comparative Example 7, and a gas barrier film C-13 ofComparative Example 8 were respectively formed in the same methods asExample 1, Example 2, Comparative Example 1, Comparative Example 2, andComparative Example 3, respectively, except that the plastic basematerials and inorganic layers were formed in the following methods.

A polyethylene naphthalate film (a PEN film, a thickness of 100 μm,Product Name: Teonex Q65FA manufactured by Teijin DuPont Films JapanLimited) was cut in a 20 cm square, and then the barrier layers in thefollowing orders were formed on the smoothing surface sides thereof.

The reactive sputtering was performed using a sputter apparatus underthe following conditions to deposit a SiNH layer having a thickness of50 nm on the substrate film. Similarly, the third barrier layer wasformed on the second barrier layer.

Film Formation Condition:

Plasma generation gas: Argon, nitrogen

Gas flow rate: Argon 100 sccm, Nitrogen 60 sccm

Target material: Si

Electricity level: 2.5 kW

Vacuum chamber internal pressure: 0.15 Pa (0.75 millitorr)

For the gas barrier films C-1 and C-2, and the gas barrier films C-11,C-12, and C-13 for comparisons, the layer configurations other than thesubstrates are listed in the following Table 5. In addition, the resultsof evaluating the gas barrier properties are listed in Table 6.

TABLE 5 No. Layer configuration (layer film thickness in parenthesis)C-1 SiNH film (50 nm)/polysilazane layer (300 nm)/SiNH film (50 nm) C-2SiNH film (50 nm)/polysilazane layer (300 nm)/SiNH film (50nm)/polysilazane layer (300 nm)/SiNH film (50 nm) C-11 SiNH film (50nm)/silicon oxide film (300 nm)/SiNH film (50 nm) C-12 SiNH film (50nm)/organic layer (300 nm)/SiNH film (50 nm) C-13 SiNH film (50nm)/polysilazane layer (300 nm)

TABLE 6 Conversion condition of polysilazane coating film HeatingIrradiation Rank of No. temperature time WVTR Bending Transparency No.(° C.) (seconds) g/m² · 24 h property (%) C-1 70 5 0.003 5 92 ExampleC-2 70 5 0.007 5 91 Example C-11 — — 0.01 2 79 Comparative Example C-12— — 0.02 2 81 Comparative Example C-13 70 5 0.06 2 95 ComparativeExample

From the results listed in Table 6, it can be confirmed that as comparedwith the gas barrier films C-11, C-12, and C-13 for comparisons, the gasbarrier films C-1 and C-2 have favorable gas barrier properties (WVTR),bending resistances (bending properties), and high visible lighttransmittance.

Examples 7 to 16 and Comparative Examples 10 to 12

The gas barrier films D-1 to N-1 of Examples 7 to 16 were formed in thesame methods as Example 1, except that the plastic base materials andinorganic layers were formed in the following methods.

In addition, a gas barrier film D-11 of Comparative Example 7, a gasbarrier film D-12 of Comparative Example 8, and a gas barrier film D-13of Comparative Example 9 were formed in the same methods as ComparativeExample 1, Comparative Example 2, and Comparative Example 3,respectively, except that the plastic base materials and inorganiclayers were formed in the following methods.

[Formation of Oxynitride Film]

Using a general CVD apparatus (PD-220NA manufactured by SAMCO Inc.) thatperforms a film formation by a capacity-binding plasma CVD method, as afirst barrier layer, a silicon oxynitride film having a film thicknessof 100 nm was formed on a plastic substrate. As a third barrier layer,similarly, a silicon oxynitride film having a thickness of 100 nm wasformed on a polysilazane layer.

As a plastic substrate, a polyethylene naphthalate film (a PEN film, athickness of 100 μm, Product Name: Teonex Q65FA manufactured by TeijinDuPont Films Japan Limited) was used. In addition, the area of thesubstrate was to be 300 cm².

The substrate is set at a predetermined location in the vacuum chamber,and then a vacuum chamber was closed. Subsequently, the inside of thevacuum chamber was exhausted, and then, at the point for the pressure tobe 0.01 Pa, a silane gas (5% nitrogen dilution), an oxygen gas (5%nitrogen dilution), and a nitrogen gas were introduced as a reactivegas. In addition, the flow rates of a silane gas, an oxygen gas, and anitrogen gas were set to be the same as disclosed in Table 7 for therespective gas barrier films. In addition, the exhaust of inside of thevacuum chamber was adjusted such that the pressure in the vacuum chamberwas to be the same as disclosed in Table 7 for the respective barrierfilms. In addition, in order to change the composition ratios for thegas barrier films D-1 to N-1, the reactive gas flow rates were adjustedas listed in Table 7.

TABLE 7 Flow rate Flow rate Flow rate Film of silane of oxygen of N₂formation gas gas gas pressure No. [sccm] [sccm] [sccm] [Pa] Example D-150 2.5 150 100 E-1 50 2.5 150 166 F-1 50 1.25 150 100 G-1 50 0.5 150 100H-1 50 5 150 100 I-1 50 6.25 150 100 J-1 50 5 150 133 K-1 50 1.25 15066.6 L-1 50 2.5 150 50 N-1 50 5 150 166 Comparative D-11 50 2.5 150 100Example D-12 50 2.5 150 100 D-13 50 2.5 150 100

For the gas barrier films D-1 to N-1, and the gas barrier films D-11,D-12, and D-13 for comparisons, the layer configurations other than thesubstrates are listed in the following Table 8. In addition, the resultsof evaluating the gas barrier properties are listed in Table 9.

TABLE 8 No. Layer configuration (layer film thickness in parenthesis)D-1 to SiO_(x)N_(y) film (100 nm)/polysilazane layer (300nm)/SiO_(x)N_(y) N-1 film (100 nm) D-11 SiO_(x)N_(y) film (100nm)/silicon oxide film (300 nm)/SiO_(x)N_(y) film (100 nm) D-12SiO_(x)N_(y) film (100 nm)/organic layer (300 nm)/SiO_(x)N_(y) film (100nm) D-13 SiO_(x)N_(y) film (100 nm)/polysilazane layer (300 nm)

TABLE 9 Conversion condition of polysilazane coating film HeatingIrradiation Composition ratio temperature time of oxynitride film WVTRRank of Bending Transparency No. (° C.) (seconds) Si:O:N O/N g/m² · 24 hproperty (%) D-1 70 5 1:0.82:0.79 1 0.003 5 95 Example E-1 70 51:0.82:0.80 1 0.005 4 90 F-1 70 5 1:0.33:1.11 0.3 0.006 4 89 G-1 70 51:0.18:1.2 0.15 0.007 3 86 H-1 70 5 1:1.49:0.33 4.5 0.004 4 90 I-1 70 51:1.54:0.28 5.5 0.007 3 88 J-1 70 5 1:1.52:0.31 4.9 0.007 3 88 K-1 70 51:0.30:1.14 0.26 0.007 3 87 L-1 70 5 1:0.77:0.66 1.1 0.002 5 94 N-1 70 51:1.44:0.33 4.4 0.002 5 95 D11 — — 1:0.82:0.79 1 0.01 2 79 ComparativeExample D12 — — 1:0.82:0.79 1 0.01 2 81 Comparative Example D13 70 51:0.82:0.79 1 0.008 2 96 Comparative Example

From the results listed in Table 9, it can be confirmed that as comparedwith the gas barrier films D-11, D-12, and D-13 for comparisons, the gasbarrier films D-1 to N-1 have favorable gas barrier properties (WVTR),bending resistances (bending properties), and high visible lighttransmittance.

<<Evaluation of Organic EL Element>>

Examples 17 to 26 and Comparative Examples 13 to 15

Formation of organic EL element

(1) Preparation of Organic EL Element Substrate

A conductive glass substrate having an ITO film (surface resistivityvalue: 10Ω/□, a thickness of 0.6 mm) as an organic EL substrate wasrinsed with 2-propanol and then subjected to a UV-ozone treatment for 10minutes. The following organic compound layers were successivelyvapor-deposited on this substrate (anode) by a vacuum vapor depositionmethod.

(First Hole Transport Layer)

Copper phthalocyanine: a film thickness of 10 nm

(Second Hole Transport Layer)

N,N′-diphenyl-N,N′-dinaphthylbenzidine: a film thickness of 40 nm

(Light-Emitting Layer/Electron Transport Layer)

Iris (8-hydroxyquinolinato) aluminum: a film thickness of 60 nm

Finally, lithium fluoride having a film thickness of 1 nm and metalaluminum having a film thickness of 100 nm were successivelyvapor-deposited to form a cathode, and then a silicon nitride filmhaving a film thickness of 5 μm was applied thereon by a plane-parallelplate CVD method, thereby preparing an organic EL element.

(2) Installment of Gas Barrier Film

The organic EL elements were sealed using each of the gas barrier filmsD-1 to N-1 prepared in Examples 7 to 16 and the gas barrier films D-11,D-12, and D-13 prepared in Comparative Examples 10 to 12 as a sealingfilm. In detail, the gas barrier film was overlapped on the element sideof the organic EL element using a thermosetting resin such that thebarrier surface side came in contact with the organic EL element side,and the organic EL element was sealed by laminating with a vacuumlaminator installed in a nitrogen purge glove box, and then heating theorganic EL element at 100° C. for 1 hour.

(3) Method of Evaluating Organic EL Element

The durability of the organic EL element prepared as described above wasevaluated by the following method.

(Accelerated Deterioration Treatment)

The element produced as described above was left for 750 hours under theenvironment of 60° C. and 90% RH, followed by carrying out a counting ofthe number of the dark spot (a non-light-emitting part) as describedbelow, together with organic EL elements that had not been subjected tothe accelerated deterioration treatment. In other words, an electriccurrent of 1 mA/cm² was applied to each of the organic El elements thathad been subjected to the accelerated deterioration treatment (“after750 hours” in Table 10) and the organic EL elements that had not beensubjected to the accelerated deterioration treatment (“initial stage” inTable 10) and light was continuously emitted for 24 hours, followed bymagnifying a part of a panel by a 100-time microscope (MS-804manufactured by Moritex Corporation, lens MP-ZE25-200) to bephotographed. A captured image was cut into a 2 mm square part, and thenthe number of dark spots (a non-light-emitting part) was counted. Theresults thereof are listed in Table 10. In addition, in Table 10, whenthe number of dark spots is not changed, it is determined as “OK” andwhen it is increased, it is determined as “NG.”

TABLE 10 Number of Number of dark spots dark spots No. Initial stageAfter 750 hours Decision D-1 0 0 OK E-1 1 1 OK F-1 1 1 OK G-1 1 1 OK H-11 1 OK I-1 1 1 OK J-1 1 1 OK K-1 1 1 OK L-1 1 1 OK N-1 1 1 OK D-11 5 19NG D-12 5 22 NG D-13 5 20 NG

As clearly listed in the above Table 10, it can be confirmed that forthe organic EL elements having the gas barrier films D-1 to N-1according to the present invention, the change of the number of the darkspots is few and excellent durability is exhibited, as compared with theorganic EL elements having the gas barrier films D-11 and D-12 inComparative Examples.

The present application is based on Japanese Patent Application No.2012-101644 filed on Apr. 26, 2012, and its disclosure is incorporatedherein by reference in its entirety.

1. A gas barrier film comprising: a substrate, and a gas barrier unitbeing arranged on at least one side of the substrate, wherein the gasbarrier unit comprises a first barrier layer including an inorganicsubstance, a second barrier layer obtained by performing a conversiontreatment to a coating film formed by coating polysilazane onto thefirst barrier layer, and a third barrier layer including an inorganicsubstance in order.
 2. The gas barrier film according to claim 1,wherein the conversion treatment is a treatment of irradiating vacuumultraviolet rays.
 3. The gas barrier film according to claim 1, whereinthe gas barrier units are repeatedly arranged.
 4. The gas barrier filmaccording to claim 1, wherein the inorganic substance is at least onekind of oxide, nitride, or oxynitride of at least one kind of Si and Al.5. The gas barrier film according to claim 1, wherein the first andthird barrier layers are formed by any one method of a chemical vapordeposition method, a physical vapor deposition method, and an atomiclayer deposition method.
 6. The gas barrier film according to claim 5,wherein the first and third barrier layers are formed by an atomic layerdeposition method.
 7. An electronic device using the gas barrier filmaccording to claim 1.